Photoluminescence study of Sb-doped ZnO films deposited by a closed tube CVT technique -通信作者

氮化镓纳米粒子的制备及光致发光研究沈龙海;富松;石广立【摘要】采用直接氮化法制备出尺寸不同的GaN纳米粒子,分别利用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和光致发光(PL)谱测试手段对所制样品进行表征和发光特性的研究.结果表明:所制备的两种GaN纳米粒子直径分别为100 nm和300 nm左右.在GaN纳米粒子的PL谱中,中心在357 nm的发射源于本征发光,中心在385 nm的发射带源于浅施主能级到价带的辐射复合,中心在560 nm左右的发射带源于浅施主能级到深受主能级间的施主-受主对辐射发光.【期刊名称】《发光学报》【年(卷),期】2014(035)005【总页数】4页(P585-588)【关键词】GaN纳米粒子;直接氮化法;光致发光【作者】沈龙海;富松;石广立【作者单位】沈阳理工大学理学院,辽宁沈阳110159;沈阳理工大学理学院,辽宁沈阳110159;沈阳理工大学理学院,辽宁沈阳110159【正文语种】中文【中图分类】O471.4;O482.311 引言GaN是一种优异的直接带隙半导体材料,室温下禁带宽度为3.4 eV,具有优良的光电性能、热稳定性及化学稳定性,是制作高亮度蓝绿发光二极管(LED)、激光二极管(LD)以及大功率、高温、高速和恶劣环境条件下工作的光电子器件的理想材料[1-2]。

最近有报道发现GaN基纳米材料具有吸收可见光使水解离产生氢的性能,这使得GaN纳米材料的研究获得了很多的关注[3-4]。

半导体纳米粒子由于小尺寸效应,往往会呈现不同于体材料的发光特性[5]。

但要实现高效可靠的光发射,尤其是可在柔性衬底上制作器件并可供日常使用的光发射材料仍然是个巨大的挑战[6]。

这使得GaN纳米材料的发光特性、能带结构及深能级行为的研究对其在未来纳米器件上的应用具有十分重要的现实意义。

目前,合成GaN纳米粒子方法主要有氨热法[7]、金属有机化合物化学气相沉积(MOCVD)法[8]、高温热解法[9-10]、胶体化学法[11]等。

Enhanced Photocatalytic Hydrogen Evolution over Cu-Doped ZnIn 2S 4under Visible Light IrradiationShaohua Shen,Liang Zhao,*Zhaohui Zhou,and Liejin GuoState Key Laboratory of Multiphase Flow in Power Engineering,Xi’an Jiaotong Uni V ersity,Xi’an,ShaanXi 710049,P.R.ChinaRecei V ed:May 22,2008;Re V ised Manuscript Recei V ed:July 25,2008A series of Cu-doped ZnIn 2S 4photocatalysts has been synthesized by a facile hydrothermal method,with the copper concentration varying from 0wt%to 2.0wt%.The physical and photophysical properties of these Cu-doped ZnIn 2S 4photocatalysts were characterized by X-ray diffraction (XRD),photoluminescence spectroscopy (PL),scanning electron microscopy (SEM),and UV -visible diffuse reflectance spectroscopy (UV -vis).The diffuse reflectance and photoluminescence spectra of Cu-doped ZnIn 2S 4shifted monotonically to longer wavelengths as the copper concentration increased from 0wt%to 2.0wt%,indicating that the optical properties of these photocatalysts greatly depended on the amount of Cu doped.Meanwhile,the layered structure of ZnIn 2S 4would be destructed gradually by Cu doping.The photoactivity of ZnIn 2S 4was enhanced when Cu 2+was doped into the crystal structure.The highest photocatalytic activity was observed on Cu (0.5wt%)–doped ZnIn 2S 4,with the rate of hydrogen evolution to be 151.5µmol/h under visible light irradiation (λ>430nm).On the basis of the calculated energy band positions and optical properties,the effect of copper as a dopant on the photocatalytic activity of Cu-ZnIn 2S 4was studied.1.IntroductionPhotocatalytic water splitting into H 2and O 2using semicon-ductor photocatalysts has been regarded as an attractive solution to resolve the global energy and environmental problems.Many effective photocatalysts have been developed;however,most of them only work in the ultraviolet region because of their wide band gap.1-4Thus,developing highly active photocatalysts with visible light response to use solar energy is important,as the ultraviolet light occupies only 2-3%of solar energy.Over the past few years,considerable effort has been made to narrow the band gap of catalysts to improve visible light response.Recent progress includes single-phase oxide PbBi 2Nb 2O 9for isopropyl alcohol degradation and water de-composition,5GaN-ZnO solid solution,6and titanium disilicide 7for pure water decomposition to H 2and O 2.One effective way to increase the absorption of photocatalyst is to form donor levels in the forbidden band by introducing foreign elements into active photocatalysts with a wide band gap.TiO 2codoped with Ni and Ta,8ZnS doped with Cu or Ni,9,10and ZnS codoped with Pb and halogens 11have been reported as active photocata-lysts under visible-light irradiation.In particular,the InTaO 4doped with Ni was found to be an active photocatalyst for overall water splitting in the visible light region.12On the other hand,chalcogenides such as CdS have been studied extensively,since they have ideal edge positions of the valence and conduction bands for hydrogen production from aqueous electrolyte solutions containing a sacrificial agent (Na 2S or/and Na 2SO 3)under visible light irradiation.13,14Unfortunately,they also have a fatal disadvantage of photocorrosion,i.e.,photogenerated holes in the valence band tend to react with chalcogenides themselves.15Although incorporation of chalco-genides into interlayers 16or mesoporous materials 17,18was efficient for stabilizing the chalcogenides and producing hy-drogen from water,the photocatalytic efficiency is still low.Recently,some multicomponent metal sulfides have been reported to be more stable and show higher photocatalytic activity under visible light.19-21Moreover,the CdZnS doped with Cu showed greatly improved stability and photocatalytic activity even without Pt as a cocatalyst.22Ternary sulfide ZnIn 2S 4,as the only member of the AB 2X 4family semiconductor with a layered structure,has attracted far-ranging interests because of its potential applications in different fields such as charge storage,23thermoelectricity,24and photo-conduction.25In 2003,Lei et al.26synthesized ZnIn 2S 4by a simple hydrothermal method and first treated ZnIn 2S 4as an efficient visible-light-driven photocatalyst for hydrogen produc-tion.In 2006,Gou et al.27hydrothermally prepared the ZnIn 2S 4solid or hollow microspheres in the presence of a surfactant such as cetyltrimethylammonium bromide (CTAB)or poly(eth-ylene glycol)(PEG).In our previous research,28,29the photo-catalytic activity of ZnIn 2S 4could be further enhanced when hydrothermally prepared in the presence of CTAB.Thus,ZnIn 2S 4turned to be a good candidate for hydrogen production from water under visible light.In the present study,a series of ZnIn 2S 4doped with different amounts of Cu was synthesized by a CTAB-assisted hydrothermal method.The effects of Cu doping on the morphology,optical properties,and photocatalytic activities of ZnIn 2S 4were discussed in detail.2.Experimental Section2.1.Synthesis of Cu-Doped ZnIn 2S 4.All chemicals are of analytical grade and used as received without further purifica-tion.ZnIn 2S 4products were prepared by a hydrothermal synthetic method.27In a typical procedure,0.735g of ZnSO 4·7H 2O,1.615g of In(NO 3)3·4H 2O,0.65g of cetyltrimethylam-monium bromide (CTAB),and a double excess of thioacetamide (TAA)were dissolved in 50mL of distilled water.The mixed solution was then transferred into a 70-mL Teflon-lined auto-clave.The autoclave was sealed and kept at 160°C for 12h*To whom correspondence should be addressed.Phone:+86-29-82668287.Fax:+86-29-82669033.E-mail address:lzhao@.J.Phys.Chem.C 2008,112,16148–161551614810.1021/jp804525q CCC:$40.75 2008American Chemical SocietyPublished on Web 09/20/2008and then cooled to room temperature naturally.A yellow precipitate was obtained,which was then filtered and washed with absolute ethanol and distilled water for several times.After being dried in a vacuum at 80°C,ZnIn 2S 4was obtained.For the synthesis of Cu-doped ZnIn 2S 4,a desired amount of 0.1M Cu(NO 3)2solution was added into the mixed solution before transferring into the autoclave.ZnIn 2S 4doped with different amounts of Cu is denoted as Cu(X )-ZnIn 2S 4;the value of X ,from 0wt%to 2.0wt%,is used to describe the weight content of Cu.2.2.Characterization.The X-ray diffraction (XRD)patterns were obtained from a PANalytical X’pert MPD Pro diffracto-meter using Ni-filtered Cu K R irradiation (Wavelength 1.5406Å).The diffuse reflection of the samples was determined by a Hitachi U-4100UV -vis -near-IR spectrophotometer.The analysis of photoluminescence spectra (PL)was carried out at room temperature using a PTI QM-4fluorescence spectropho-tometer.The sample morphology was observed by a JEOL JSM-6700FE scanning electron microscope.2.3.Evaluation of Photocatalytic Activity.Photocatalytic hydrogen evolution was performed in a gas-closed circulation system with a top window Pyrex cell.A 300W Xe lamp was used as the light source,and the UV part of the light was removed by a cutoff filter (λ>430nm).Hydrogen evolved was analyzed by an online thermal conductivity detector (TCD)gas chromatograph (NaX zeolite column,nitrogen as a carrier gas)every 10min.In all experiments,the photocatalyst powder (0.2g)was dispersed by a magnetic stirrer in 150mL of 0.25M Na 2SO 3/0.35M Na 2S aqueous solution.Here,Na 2SO 3/Na 2S mixed sacrificial agent was used to scavenge photogenerated holes.Nitrogen was purged through the cell before reaction to remove oxygen.Pt (1wt%)as a cocatalyst for the promotion of hydrogen evolution was photodeposited in situ on the photocatalysts from the precursor of H 2PtCl 6·6H 2O.The tem-perature for all the photocatalytic reactions was kept at 25(0.5°C.The blank experiments showed no appreciable H 2evolution in the absence of irradiation or photocatalyst.Apparent quantum yield defined by the eq 1was measured using a 420nm band-pass filter and an irradiatometer.A.Q.Y.(%))the number of reacted electronsthe number of incident photons×100)the number of evolved H 2molecules ×2the number of incident photons×100(1)2.4.Band Structure Calculation.The plane-wave-based density functional theory (DFT)calculation was carried out for ZnIn 2S 4with hexagonal structure by employing the CASTEPprogram to obtain further information about the energy structure of the Cu-ZnIn 2S 4photocatalysts.30The core electrons were treated using ultrasoft pseudopotentials,31and the valence electronic configurations for Zn,In,and S are 3d 104s 2,4d 105s 25p 1,and 3s 23p 4,respectively.The kinetic energy cutoff was taken to be 400eV for ZnIn 2S 4.The exchange and correlation interactions were modeled using the generalized gradient approximation (GGA).The calculation was carried out using the primitive unit cell of [ZnIn 2S 4]2,which had 31occupied orbitals.The atomic coordinates of ZnIn 2S 4were obtained from Gou et al.273.Results and Discussion3.1.Crystal Structure.Figure 1A shows X-ray diffraction patterns of Cu(X )-ZnIn 2S 4photocatalysts (X )0wt%to 2.0wt%).Without Cu doping,the diffraction peaks of the obtained ZnIn 2S 4sample can be readily indexed as a pure phase hexagonal ZnIn 2S 4(ICSD-JCPDS card No.01-072-0773,a )3.85Å,c )24.68Å),and no other impurities such as ZnS,In 2S 3,oxides,or organic compounds related to reactants were detected.When ZnIn 2S 4was doped with Cu,the XRD patterns of the obtained Cu(X )-ZnIn 2S 4were almost the same as that of the hexagonal ZnIn 2S 4,except that the diffraction peaks were slightly shifted to higher angles with the amount of Cu doped increasing,as shown in Figure 1B.This observation suggested that Cu 2+was homogeneously incorporated into the lattice of ZnIn 2S 4,because the ionic radius of Cu 2+(0.72Å)is smaller than the radius of Zn 2+(0.74Å)and In 3+(0.81Å).32Furthermore,Cu 2+may occupy the Zn 2+site,since charge compensation was very easy in this case,as deduced by Shionoya et al.33An XRD pattern of CuS around 2θ)30°could be easily observed while the amount of Cu doped was close to 2.0wt%.This was due to the limitation of doping amount in the ZnIn 2S 4lattice.113.2.Morphology.Figure 2shows SEM images for Cu(X )-ZnIn 2S 4with X )0wt%to 2.0wt%.During the hydrothermal process,addition of Cu ion directly affects the morphology of Cu-ZnIn 2S4.When none of the Cu was doped,ZnIn 2S 4exhibited a lot of separate microspheres with diameters of 1-2µm,as shown in Figure 2a.Further observation showed that all the microspheres were composed of numerous petals/sheets.This growth tendency of lamellar structures might be related to the layered feature of hexagonal ZnIn 2S 4.27When X )0.1wt%to 0.5wt %,ZnIn 2S 4products still appeared in the shape of microspheres;however,increasing the amount of Cu doped led to gradual decrease in the diameter of Cu(X )-ZnIn 2S 4micro-spheres.The diameter of microsphere was about 0.5-1µmforFigure 1.X-ray diffraction patterns of Cu(X )-ZnIn 2S 4;the values of X were (a)0.0wt%,(b)0.1wt%,(c)0.3wt%,(d)0.5wt%,(e)0.7wt%;(f)0.9wt%,(g)1.2wt%,(h)1.6wt%,(i)2.0wt%.Enhanced Photocatalytic Hydrogen Evolution J.Phys.Chem.C,Vol.112,No.41,200816149Figure 2.Part 1of 2.16150J.Phys.Chem.C,Vol.112,No.41,2008Shen et al.Cu(0.5wt%)-ZnIn 2S 4.As X increased further,the shape of microspheres for Cu(X )-ZnIn 2S 4was destructed partially and even throughly,as shown in Figure 2e -g,as well as the petals/sheets presented to be more irregular.When X )1.6wt%to 2.0wt %,instead of microspheres and petals/sheets,Cu(X )-ZnIn 2S 4turned out to be a bulky conglomeration with a rough surface,and petals/sheets could be hardly observed.The morphology of the Cu(X )-ZnIn 2S 4samples obtained in the same synthetic condition varies regularly with the increasing amount of Cu doped.That is to say,the layered structure of hexagonal ZnIn 2S 4,as well as the shape of microspheres,could be destructed gradually by the increasing Cu dopant.3.3.Optical Properties.Figure 3shows the UV -vis diffuse reflectance spectra of Cu(X )-ZnIn 2S 4with X )0wt%to 2.0wt%.The onset of the absorption edge of ZnIn 2S 4was at about 495nm,corresponding to the band gap of 2.51eV.Moreover,ZnIn 2S 4had an intense absorption band with a steep edge in the visible-light region.This shape indicated that the UV -vis absorption was due to the band gap transition but not due to the transition from impurity levels to the conduction band of ZnIn 2S4.As X increased,a new absorption shoulder around 500nm was observed,and the absorption edge of Cu(X )-ZnIn 2S 4shifted monotonously from 575to 650nm with an increase inX from 0.1wt%to 1.2wt%,corresponding to the narrowing of the band gap from 2.16to 1.91eV.The absorption shoulder with a long tail on the low energy side,which was characteristic of doped photocatalysts 34,35and indicated that intraband gap states were formed by the dopants in the forbidden band,couldFigure 2.Part 2of 2.Scanning electron microscope images of Cu(X )-ZnIn 2S 4;the values of X were (a)0.0wt%,(b)0.1wt%,(c)0.3wt%,(d)0.5wt%,(e)0.7wt%;(f)0.9wt%,(g)1.2wt%,(h)1.6wt%,(i)2.0wt%.Figure 3.Diffuse reflectance spectra of Cu(X )-ZnIn 2S 4;the values of X were (a)0.0wt%,(b)0.1wt%,(c)0.3wt%,(d)0.5wt%,(e)0.7wt%;(f)0.9wt%,(g)1.2wt%,(h)1.6wt%,(i)2.0wt%.Enhanced Photocatalytic Hydrogen Evolution J.Phys.Chem.C,Vol.112,No.41,200816151be assigned to the transition from the Cu3d level above the valence band to the conduction band of ZnIn 2S 4.In addition,a broad band (λ>750nm)was observed for Cu (1.6wt%to 2.0wt%)-ZnIn 2S 4.This was due to the impurity CuS phase,as indicated by X-ray diffraction.The PL spectra of Cu(X )-ZnIn 2S 4,with X )0wt%to 2.0wt%,were obtained using an excitation wavelength of 330nm,as shown in Figure 4.The PL intensity and response range of Cu(X )-ZnIn 2S 4were influenced by Cu doping.The PL spectra,in company with the diffuse reflect spectra,shifted successively to longer wavelength with the change in the amount of Cu doped,indicating that the energy structure of Cu(X )-ZnIn 2S 4depended on the value of X.Similar phenomena has been reported by Kudo et al.in the (AgIn)x Zn 2(1-x )S 2solid solutions.19However,as shown in Table 1,the emission spectra of Cu(X )-ZnIn 2S 4(X )0.0wt%to 0.7wt%)was somewhat red-shifted vis-a-vis the absorption edge.This is because the PL emission of Cu(X )-ZnIn 2S 4presented here is broadband,36or donor -acceptor defect (such as sulfur vacancy)based,37in nature.In constrast,the absorption edge of Cu(X )-ZnIn 2S 4(X )0.9wt%to 2.0wt%)shifted to longer wavelength when compared to the emission spectra.This may be due to the excess of Cu doping,resulting in the formation of CuS,which has a total absorption in the visible-light region.Thus,as reported by Peng et al.on Cu-ZnS,38the PL emission of Cu(X )-ZnIn 2S 4may arise from the recombination between the shallow donor level (sulfur vacancy)and the t 2level of Cu 2+(splitting from Cu3d).As the energy level of sulfur vacancy relative to the valence band nearly stays constant in these samples despite the variation in Cu 2+concentration,it can be concluded that the t 2energy level ofCu 2+ions is farther from the valence band with increasing Cu 2+concentration.In addition,it could be found from Figure 4that the PL intensity of Cu(X )-ZnIn 2S 4gradually increased as the Cu content increased and arrived at the highest degree when the Cu content was 0.5wt%.While the Cu content continued to increase,namely more than 0.5wt%,the PL intensity began to decrease.In Mn-ZnS 39and Cu-ZnS,38a similar photolumi-nescence phenomenon was also observed,which can be explained by the effect of ion doping.As the foregoing analysis shows,these PL spectra were related to native defects (e.g.,sulfur vacancy).When Cu 2+was doped into ZnIn 2S 4,more defect states would be introduced.Therefore,it is reasonable that the defect-related PL intensities were enhanced for the Cu 2+-doped samples compared with the undoped sample.As for the decrease of the PL intensity with the Cu 2+concentration above 0.5wt%,it may be caused by the formation of CuS,though the XRD measurement did not detect the existence of the copper sulfide phase.In Eu-doped GaN,40a similar concentration quenching phenomenon was also observed,which was mainly attributed to the formation of EuN compound.3.4.Band Structures.Figure 5A shows the band structure and the density of state (DOS)of ZnIn 2S 4.The density contour maps for the lowest unoccupied molecular orbitals (LUMO)and highest occupied molecular orbitals (HOMO)of ZnIn 2S 4are shown in Figure 5B.We can observe clearly that both the top of valence band and the bottom of the conduct band lay at the G point of the Brillouin zone from Figure 5A.So the pure ZnIn 2S 4crystal is a direct gap band semiconductor.The theoretical value of the direct gap at G is 0.4eV,which is less than the experimental value of about 2.51eV.Such an underestimation of the band gap is a well-known artifact of GGA.The density of states (Figure 5A)indicates that the S3p orbitals make a significant contribution to the valence band top of ZnIn 2S 4and that the highest occupied molecular orbital (HOMO)levels are composed mainly of the hybridized S3p and Zn3d orbitals.The In5s orbitals locate at more negative energy levels than that of S3p orbitals and do not contribute much to the valence band top.The lowest unoccupied molecular orbital (LUMO)levels are composed mainly of the In5s5p and S3p orbitals.The Zn4s4p orbitals locate at more positive energy levels and do not contribute much to the conduction band bottom.Based on the optical properties and DFT calculations,the schematic energy level diagram of Cu(X )-ZnIn 2S 4is shown in Figure 6.As for ZnIn 2S 4,upon photoexcitation,electrons would transfer from the valence band (hybridized S3p and Zn3d orbitals)to the conduction band (hybridized In5s5p and S3p orbitals),leaving photogenerated holes in the valence band.As aforementioned,the PL emission has been known to be due to the photoluminescence transition from the sulfur-vacancy-related donor level or the conduction band to the valence band.Therefore,the energy difference between the absorption edge and the emission spectra of ZnIn 2S 4can be explained.Taking the Cu doping into account,the t 2state,splitting from discrete Cu3d levels,will form above the edge of valence band of ZnIn 2S 4,which is consistent with those reported by Peng 38and Xu 41in Cu-ZnS.A similar orbital-splitting phenomenon has been observed by Ye 42and Zou 43for Cr-3d and Ni-3d orbtials in In 12NiCr 2Ti 10O 42and Ca 2NiWO 6.The t 2(Cu3d)level,pro-duced by doping Cu 2+into ZnIn 2S 4,works as the donor level and acceptor level for photoexcitation and PL emission,respec-tively,44as shown in Figure 6.With the amount of Cu doped increasing,the t 2(Cu3d)level will be elevated farther fromtheFigure 4.Photoluminescence spectra of Cu(X )-ZnIn 2S 4;the values of X were (a)0.0wt%,(b)0.1wt%,(c)0.3wt%,(d)0.5wt%,(e)0.7wt%;(f)0.9wt%,(g)1.2wt%,(h)1.6wt%,(i)2.0wt%,excited at 330nm.TABLE 1:Band Gap,Absorption Edge,PL Emission and Emission Intensity of Cu(X )-ZnIn 2S 4,with X )0.0wt%to 2.0wt%X (wt%)band gap a (eV)absorption edge (nm)PL emission (nm)emission intensity(normalized,a.u.)0.0 2.514955600.330.1 2.165755970.720.3 2.115876110.760.5 2.05604617 1.000.7 2.026146260.740.9 1.946396320.561.2 1.916506390.421.6 1.737156550.202.01.657506660.19aCalculated from absorption edge.16152J.Phys.Chem.C,Vol.112,No.41,2008Shen et al.valence band,which results in the redshift of absorption edge and PL emission for Cu(X )-ZnIn 2S 4.3.5.Photocatalytic Activities of Cu(X )-ZnIn 2S4.Figure 7shows the dependence of photocatalytic H 2evolution from an aqueous Na 2SO 3/Na 2S solution over Cu(X )-ZnIn 2S 4under visible-light irradiation (λ>430nm).Either nondoped orCu-Figure 5.(A)Band structure and density of states for ZnIn 2S 4calculated by the density functional method.(B)Density contour maps for the LUMO and HOMO of ZnIn 2S 4.Figure 6.Schematic energy level diagram of Cu(X )-ZnIn 2S 4.Vs stands for sulfurvacancy.Figure 7.Photocatalytic H 2evolution under visible-light irradiation over Cu(X )-ZnIn 2S 4;the values of X were (a)0.0wt%,(b)0.1wt%,(c)0.3wt%,(d)0.5wt%,(e)0.7wt%,(f)0.9wt%,(g)1.2wt%,(h)1.6wt%,(i)2.0wt%.Enhanced Photocatalytic Hydrogen Evolution J.Phys.Chem.C,Vol.112,No.41,200816153doped ZnIn 2S 4was active and stable for splitting water to hydrogen.The rate of H 2evolution over nondoped ZnIn 2S 4was 26.1µmol ·h -1.The apparent quantum yield at 420nm was calculated to be 9.6%by eq 1.As the amount of doped Cu was increased,the photocatalytic activity of Cu(X )-ZnIn 2S 4was increased,because the visible-light absorption band of Cu(X )-ZnIn 2S 4grew.11The highest activity was obtained when 0.5wt %of Cu was doped,the rate of hydrogen evolution reached at 151.5µmol ·h -1,with the apparent quantum yield determined to be 14.2%.As the concentration of Cu doped was above 0.5wt%,the activity was decreased,though the visible-light absorption band grew further.Such a similar dependence of photocatalytic H 2evolution upon the amount of dopant has been observed for several other photocatalysts.11,44,45These observa-tions indicated that the photocatalytic activites depended upon not only the visible-light absorption (i.e.,band gap)but also some other factors.One of the reasons for the decrease in photocatalytic activity may be due to the impurity phase of CuS,resulted from the excess of Cu doping,as proved by XRD results.The CuS impurity may work as recombination sites between photogenerated electrons and holes.Another possible inactivation factor for the ZnIn 2S 4doped with excessive Cu is that the layered structure could be destructed gradually with the amount of Cu increased further,as revealed by SEM images.Some perovskite photocatalysts with layered structure have also shown good photocatalytic activity for splitting water to hydrogen,as the dipole moment along layers seems to enhance the charge separation,resulting in high activity.46,47Figure 8shows the photocatalytic activity and photolumi-nescence intensity as a function of Cu content in the Cu(X )-ZnIn 2S 4.The change in photoluminescence intensity was concurrent to that in photocatalytic activity,as both photolu-minescence intensity and photocatalytic activity reached the highest level when 0.5wt %of Cu was doped.Photolumines-cence depends on various factors such as the densities of photoexcited charges and recombination centers,the extent of nonradiation process,and the mobility of photoexcited charges.44It is difficult to determine which process is mainly responsible for changes in photoluminescence intensity with Cu content.However,in association with the change in photocatalytic activity,a plausible explanation can be made as follows.During the PL process,vacancies (such as sulfur vacancy)and defects can easily bind photoinduced electrons to form excitons,so that the PL signal can easily occur.48When Cu 2+ions were doped into ZnIn 2S 4,more vacancies (such as sulfur vacancy)or defect states would be introduced.38The larger the content of vacancy or defect,the stronger the PL signal.Meanwhile,an increasein Cu content not only raised the t 2(Cu3d)level to narrow the band gap of Cu(X )-ZnIn 2S 4,which has been demonstrated by the UV -vis diffuse reflectance spectra,but also enhanced the density of the t 2(Cu3d)levels and increased the concentration and the mobility of the photoexcited electrons.44These could be related to the enhancement of photocatalytic activity.However,further increase in the amount of Cu doped would result in the increased absorption to longer wavelength,which was likely due to the formation of CuS,as discussed previously.Thus,the CuS impurity weakened the photoluminescence,40as well as lowered photocatalytic activity of Cu-doped ZnIn 2S 4.114.ConclusionsIn summary,we have synthesized a series of Cu-doped ZnIn 2S 4photocatalysts by a simple hydrothermal method.The photocatalytic activity of ZnIn 2S 4was remarkably enhanced by Cu doping.The optimized Cu (0.5wt%)-doped ZnIn 2S 4photocatalyst showed the highest activity for splitting water into H 2,with the rate of hydrogen evolution to be 151.5µmol ·h -1.With increasing concentration of Cu doped,the UV -vis spectra and PL emission peak were systematically shifted to longer wavelength.Moreover,there were certain intrinsic relationships between the PL emission intensity and photocatalytic activity of Cu-doped ZnIn 2S 4.That is to say,the change in photolumi-nescence intensity was concurrent to that in photocatalytic activity,both depending on the increasing concentration of Cu doped.Acknowledgment.The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (No.50521604)and National Basic Research Program of China (No.2003CB214500).The authors also would like to thank the molecular simulating platform and National High Performance Computing Center (Xi’an)at Xi’an Jiaotong University for the calculation resource support.References and Notes(1)Domen,K.;Kudo,A.;Ohnishi,T.J.Catal.1986,102,92.(2)Hwang,D.W.;Kim,H.G.;Kim,J.;Cha,K.Y.;Kim,Y.G.;Lee,J.S.J.Catal.2000,193,40.(3)Kato,H.;Asakura,K.;Kudo,A.J.Am.Chem.Soc.2003,125,3082.(4)Sato,J.;Saito,N.;Yamada,Y.;Maeda,K.;Takata,T.;Kondo,J.N.;Hara,M.;Kobayashi,H.;Domen,K.J.Am.Chem.Soc.2005,127,4150.(5)Kim,H.G.;Hwang,D.W.;Lee,J.S.J.Am.Chem.Soc.2004,126,8912.(6)Maeda,K.;Teramura,K.;Lu,D.;Takata,T.;Saito,N.;Inoue,Y.;Domen,K.Nature 2006,440,295.(7)Ritterskamp,P.;Kuklya,A.;Wu ¨stkamp,M.;Kerpen,K.;Weidentha-ler,C.;Demuth,M.Angew.Chem.,Int.Ed.2007,46,7770.(8)Niishiro,R.;Kato,H.;Kudo,A.Phys.Chem.Chem.Phys.2005,7,2241.(9)Kudo,A.;Sekizawa,M.Catal.Lett.1999,58,241.(10)Kudo,A.;Sekizawa,mun.2000,15,1371.(11)Tsuji,I.;Kudo,A.J.Photochem.Photobiol.A 2003,156,249.(12)Zou,Z.G.;Ye,J.H.;Sayama,K.;Arakawa,H.Nature 2001,414,625.(13)Bubler,N.;Meier,K.;Reber,J.F.J.Phys.Chem.1984,88,3261.(14)Naman,S.A.;Gra ¨tzel,M.J.Photochem.Photobiol.A 1994,77,249.(15)Inoue,T.;Watanabe,T.;Fujishima,A.;Honda,K.J.Electrochem.Soc.1977,124,719.(16)Shangguan,W.;Yoshida,A.J.Phys.Chem.B 2002,106,12227.(17)Shen,S.;Guo,L.J.Solid State Chem.2006,179,2629.(18)Shen,S.;Guo,L.Mater.Res.Bull.2008,43,437.(19)Tsuji,I.;Kato,H.;Kobayashi,H.;Kudo,A.J.Am.Chem.Soc.2004,126,13406.(20)Tsuji,I.;Kato,H.;Kudo,A.Angew.Chem.,Int.Ed.2005,44,3565.(21)Jang,J.S.;Choi,S.H.;Shin,N.;Yub,C.;Lee,J.S.J.Solid State Chem.2007,180,1110.Figure 8.Dependence of photocatalytic activity for H 2evolution and PL emission intensity over Cu(X )-ZnIn 2S 4,with X )0.0wt%to 2.0wt%.16154J.Phys.Chem.C,Vol.112,No.41,2008Shen et al.(22)Liu,G.;Zhao,L.;Ma,L.;Guo,mun.2008,9,126.(23)Romeo,N.;Dallaturca,A.;Braglia,R.;Sberveglieri,G.Appl.Phys. Lett.1973,22,21.(24)Seo,W.S.;Otsuka,R.;Okuno,H.;Ohta,M.;Koumoto,K.J.Mater. Res.1999,14,4176.(25)Romeo,N.;Tarricone,L.;Zanotti,L.Il Nuo V o Cim.D1983,2, 2007.(26)Lei,Z.;You,W.;Liu,M.;Zhou,G.;Takata,T.;Hara,M.;Domen, K.;Li,mun.2003,17,2142.(27)Gou,X.;Cheng,F.;Shi,Y.;Zhang,L.;Peng,S.;Chen,J.;Shen, P.J.Am.Chem.Soc.2006,128,7222.(28)Shen S.;Zhao L.;Guo L.Mater.Res.Bull.,2008,doi:10.1016/ j.materresbull.2008.03.027.(29)Shen S.;Zhao L.;Guo L.Int.J.Hydrogen Energy,2008, doi:10.1016/j.ijhydene.2008.05.043.(30)Segall,M.D.;Lindan,P.J.D.;Probert,M.J.;Pickard,C.J.;Hasnip, P.J.;Clark,S.J.;Payne,M.C.J.Phys.:Condens.Matter2002,14,2717.(31)Vanderbilt,D.Phys.Re V.B1990,41,7892.(32)Lei,Z.;Ma,G.;Liu,M.;You,W.;Yan,H.;Wu,G.;Takata,T.; Hara,M.;Domen,K.;Li,C.J.Catal.2006,237,322.(33)Shionoya,S.;Tamoto,Y.J.Phys.Soc.Jpn.1964,19,1142.(34)Konta,R.;Ishii,T.;Kato,H.;Kudo,A.J.Phys.Chem.B2004, 108,8992.(35)Miyauchi,M.;Takashio,M.;Tobimatsu,ngmuir2004,20, 232.(36)Spanhel,I.;Anderson,M.A.J.Am.Chem.Soc.1991,113,2826.(37)Castro,S.L.;Bailey,S.G.;Raffaelle,R.P.;Banger,K.K.;Hepp,A.F.J.Phys.Chem.B2004,108,12429.(38)Peng,W.Q.;Cong,G.W.;Qu,S.C.;Wang,Z.G.Opt.Mater. 2006,29,313.(39)Ghosh,P.K.;Ahmed,Sk.F.;Jana,S.;Chattopadhyay,K.K.Opt. Mater.2007,29,1584.(40)Bang,H.;Morishima,S.;Sawahata,J.;Seo,J.;Takiguchi,M.; Tsunemi,M.;Akimoto,K.;Nomura,M.Appl.Phys.Lett.2004,85,227.(41)Xu,S.J.;Chua,S.J.;Liu,B.;Gan,L.M.;Chew,C.H.;Xu,G.Q. Appl.Phys.Lett.1998,73,478.(42)Wang,D.;Zou,Z.;Ye,J.Chem.Phys.Lett.2005,411,285.(43)Li,D.;Zheng,J.;Zou,Z.J.Phys.Chem.Solids2006,67,801.(44)Arai,N.;Saito,N.;Nishiyama,H.;Domen,K.;Kobayashi,H.;Sato, K.;Inoue,Y.Catal.Today2007,129,407.(45)Nishimoto,S.;Matsuda,M.;Miyake,M.Chem.Lett.2006,35, 308.(46)Kudo,A.;Kato,H.;Nakagawa,S.J.Phys.Chem.B2000,104, 571.(47)Hwang,D.W.;Kim,H.G.;Lee,J.S.;Kim,J.;Li,W.;Oh,S.H. J.Phys.Chem.B2005,109,2093.(48)Jing,L.;Qu,Y.;Wang,B.;Li,S.;Jiang,B.;Yang,L.;Fu,W.;Fu,H.;Sun,J.Sol.Energy Mater.Sol.Cells2006,90,1773.JP804525QEnhanced Photocatalytic Hydrogen Evolution J.Phys.Chem.C,Vol.112,No.41,200816155。

收稿日期：２０２０－１２－０８基金项目：四川省教育厅科研项目（ＪＧ２０１８－４７７）作者简介：陆春海（１９６８—），博士，教授，从事三废治理与处置、多尺度模拟研究、核燃料循环与材料檽檽檽檽檽檽檽檽檽檽檽檽檽檽殦殦殦殦。

科研与开发铝掺杂钛酸锶光催化剂的合成任金秋１，苏静倩１，吴凯霖１，陆春海１，２（１．地学核技术四川省重点实验室（成都理工大学），四川成都　６１００５９２．国家环境保护水土污染协同控制与联合修复重点实验室（成都理工大学），四川成都　６１００５９）摘要：具有独特钙钛矿结构的钛酸锶由于其独特的光学性能已经受到广泛关注。

本文尝试以廉价、无毒的铝化合物作为掺杂剂，进行铝掺杂钛酸锶光催化剂的合成。

合成的干凝胶于５００℃环境下煅烧３ｈ合成ＳｒＴｉＯ３光催化剂，表征结果显示：合成的光催化剂以立方钛酸锶型为主、部分无定形和部分金红石型ＴｉＯ２。

Ａｌ元素掺杂改进了形貌且出现部分片状形貌。

关键词：钛酸锶；铝；光催化；合成中图分类号：Ｏ６４３．３ 文献标识码：Ａ 文章编号：１００８－０２１Ｘ（２０２１）０６－０００１－０３ＳｙｎｔｈｅｓｉｓｏｆＡｌＤｏｐｅｄＳｔｒｏｎｔｉｕｍＴｉｔａｎａｔｅＰｈｏｔｏｃａｔａｌｙｓｔＲｅｎＪｉｎｑｉｕ１，２，ＳｕＪｉｎｇｑｉａｎ１，２，ＷｕＫａｉｌｉｎ１，２，ＬｕＣｈｕｎｈａｉ１，２（１．ＳｉｃｈｕａｎＫｅｙＬａｂｏｒａｔｏｒｙｏｆＡｐｐｌｉｅｄＮｕｃｌｅａｒＴｅｃｈｎｉｑｕｅｓｉｎＧｅｏｓｃｉｅｎｃｅｓ（ＣｈｅｎｇｄｕＵｎｉｖｅｒｓｉｔｙｏｆＴｅｃｈｎｏｌｏｇｙ），Ｃｈｅｎｇｄｕ　６１００５９，Ｃｈｉｎａ；２．ＳｔａｔｅＥｎｖｉｒｏｎｍｅｎｔａｌＰｒｏｔｅｃｔｉｏｎＫｅｙＬａｂｏｒａｔｏｒｙｏｆＳｙｎｅｒｇｉｓｔｉｃＣｏｎｔｒｏｌａｎｄＪｏｉｎｔＲｅｍｅｄｉａｔｉｏｎｆｏｒＳｏｉｌａｎｄＷａｔｅｒＰｏｌｌｕｔｉｏｎ（ＣｈｅｎｇｄｕＵｎｉｖｅｒｓｉｔｙｏｆＴｅｃｈｎｏｌｏｇｙ），Ｃｈｅｎｇｄｕ　６１００５９，Ｃｈｉｎａ）Ａｂｓｔｒａｃｔ：Ｓｔｒｏｎｔｉｕｍｔｉｔａｎａｔｅ（ＳＴＯ）ｈａｓａｕｎｉｑｕｅｐｅｒｏｖｓｋｉｔｅｓｔｒｕｃｔｕｒｅ．ＳＴＯａｔｔｒａｃｔｅｓｍｕｃｈａｔｔｅｎｔｉｏｎｄｕｅｔｏｉｔｓｕｎｉｑｕｅｏｐｔｉｃａｌｐｒｏｐｅｒｔｉｅｓ．Ｉｎｔｈｉｓｐａｐｅｒ，ｗｅｔｒｙｔｏｓｙｎｔｈｅｓｉｚｅａｌｕｍｉｎｕｍｄｏｐｅｄｓｔｒｏｎｔｉｕｍｔｉｔａｎａｔｅｐｈｏｔｏｃａｔａｌｙｓｔｂｙｕｓｉｎｇｃｈｅａｐａｎｄｎｏｎ－ｔｏｘｉｃａｌｕｍｉｎｕｍｃｏｍｐｏｕｎｄｓａｓｄｏｐａｎｔｓ．ＳＴＯｐｈｏｔｏｃａｔａｌｙｓｔｗａｓｓｙｎｔｈｅｓｉｚｅｄｂｙｃａｌｃｉｎａｔｉｏｎａｔ５００℃ｆｏｒ３ｈｏｕｒｓ．ＴｈｅｃｈａｒａｃｔｅｒｉｚａｔｉｏｎｒｅｓｕｌｔｓｓｈｏｗｅｄｔｈａｔｔｈｅＳＴＯｗａｓｃｕｂｉｃｓｔｒｏｎｔｉｕｍｔｉｔａｎａｔｅｗｉｔｈｐａｒｔｏｆａｍｏｒｐｈｏｕｓＳＴＯａｎｄｒｕｔｉｌｅＴｉＯ２．Ａｌｄｏｐｉｎｇｉｍｐｒｏｖｅｓｔｈｅｍｏｒｐｈｏｌｏｇｙａｎｄｓｏｍｅｌａｍｅｌｌａｒｍｏｒｐｈｏｌｏｇｙａｐｐｅａｒｓ．Ｋｅｙｗｏｒｄｓ：ｓｔｒｏｎｔｉｕｍｔｉｔａｎａｔｅ；ａｌｕｍｉｎｕｍ；ｐｈｏｔｏｃａｔａｌｙｓｉｓ；ｓｙｎｔｈｅｓｉｓ 钛酸锶（ＳｒＴｉＯ３，ＳＴＯ）具有独特钙钛矿结构，由于其独特的结构、良好的物理和化学稳定性、强烈的可见光发光和优异的光学性能而受到人们的关注。

First-principles calculations of electronic structure and optical properties of Boron-doped ZnO with intrinsicdefectsYen-Chun Peng,Chieh-Cheng Chen,Hsuan-Chung Wu ⇑,Jong-Hong LuDepartment of Materials Engineering,Ming Chi University of Technology,New Taipei 24301,Taiwana r t i c l e i n f o Article history:Received 11August 2014Received in revised form 27October 2014Accepted 27October 2014Available online 15November 2014Keywords:First principles B-doped ZnO Intrinsic defectElectronic structure Optical propertya b s t r a c tThis study adopted first-principles calculations to evaluate the effects of intrinsic defects on the elec-tronic structure and optical properties of Boron-doped ZnO (BZO).Four types of defect were considered:non-defective (B Zn ),Zn vacancies (V Zn ),O vacancies (V O ),and interstitial Zn (Zn i ).Calculations of forma-tion energy illustrate that O-rich conditions tend to induce V Zn ,while O-poor conditions tend to induce V O and Zn i .With respect to electric properties,V Zn defects in BZO decrease carrier concentration as well as mobility,which consequently decreases the conductivity of BZO.The existence of V O or Zn i defects in BZO leads to n-type conductive characteristics and increases the optical band gap.The existence of Zn i defects in BZO also increases the effective mass,which decreases the mobility and conductivity of BZO.As for the optical properties,the introduction of V Zn to BZO leads to an increase in transmittance in the visible light region,but a decrease in the UV region.The introduction of intrinsic V O and Zn i defects to BZO leads to a significant decrease in transmittance in the visible as well as UV regions.The calculated results were also compared with experimental data from the literature.Ó2014Elsevier B.V.All rights reserved.1.IntroductionZnO is an abundant,non-toxic material with a wide band gap (3.37eV)and transparent properties under visible light.ZnO has recently attracted considerable attention as an alternative for Tin-doped In 2O 3(ITO),which is currently the most common choice of transparent conductive oxide for a variety of applications [1,2].The resistivity of pure ZnO is on the order of 10À2X -cm,which is far higher than that of ITO (10À4X -cm order).A great deal of research has gone into enhancing the conductivity of ZnO through the addition of various dopants,which can mainly be divided into metals [3–5]and non-metals [6,7].B-doped ZnO (BZO)thin film shows considerable promise for its superior photoelectric proper-ties and stability [8,9].Many groups have investigated the effects of process parameters on the electric and optical properties of BZO thin film,with the aim of optimizing performance [7–13].Miyata et al.[7]indicated that the transmittance of BZO thin film could be improved through the introduction of O 2gas from 0sccm to 10sccm.David et al.[10]reported that annealing temperature and atmosphere strongly affect the conductivity of BZO.Yang et al.[11]concluded that the low oxygen partial pressure during deposition increases the carrier density of oxygen vacancies,which leads to a strong decline in resistivity.However,resistivity in sam-ples produced under the high oxygen partial pressure is far higher than in samples deposited under low oxygen partial pressure,which suggests the existence of p-type carriers of Zinc vacancies in films grown under high oxygen partial pressure.Patil et al.[12]synthesized B-doped ZnO powders using a mechanochemical method.The photoluminescence (PL)spectra at room temperature is an indication that a greater number of oxygen vacancies exist in nonmetal-doped ZnO,compared to pure ZnO.In the fabrication of BZO microrods,Yılmaz et al.[13]investigated the influence of B diffusion doping on optical emission and defect formation.PL spec-tra results revealed that the intensity of the deep level visible band emission increases with an increase in annealing time,which implies a significant increase in the concentration of intrinsic defects.As outlined above,various process conditions influence the type and number of intrinsic defects with a subsequent influence on the electric and optical properties of BZO.Gaining a comprehensive understanding of the electric and optical characteristics of BZO would require in-depth study into the effects of intrinsic defects on the properties of BZO.First-principles calculations can provide information concerning materials at the microscopic scale to eluci-date the connection between structure and properties.It is well known that the use of conventional density functional theory/10.1016/j.optmat.2014.10.0580925-3467/Ó2014Elsevier B.V.All rights reserved.⇑Corresponding author at:Department of Materials Engineering,Ming Chi University of Technology,84Gungjuan Road,Taishan,New Taipei 24301,Taiwan.Tel.:+8862290898994675;fax:+886229084091.E-mail address:hcwu@.tw (H.-C.Wu).(DFT)leads to a considerable underestimation of the calculated band gap in ZnO [14–16].In our previous study [17],we used the DFT plus Hubbard U (DFT +U)method to avoid underestimat-ing the band gap.This approach reduced the differences in calcu-lated band gap and lattice constant to within 1%of the experimental values.The current study extended the utilization of the DFT +U method to calculate and analyze the effects of intrin-sic defects (V Zn ,V O ,and Zn i )on the formation energy,crystal struc-ture,electronic structure,and optical properties of BZO.These results clarify the connections among the fabrication process,structure,and properties of BZO,for use in determining the criteria for future material designs.2.Calculation methodsThis study considered a 2Â2Â2supercell of a Wurtzite ZnO,including 16Zn atoms and 16O atoms,as shown in Fig.1.A B-monodoping model was constructed by substituting one Zn atom (number 1site)with one B atom (B Zn model),which correspond to the B concentrations of 6.25at.%.We also considered three intrinsic defects in the B Zn structure,in which Zn vacancies(B Zn V Zn ),O vacancies (B Zn V O ),and interstitial Zn (B Zn Zn i )are repre-sented as 2,3,and 4,respectively.The V Zn ,V O ,and Zn i concentra-tions corresponds to doping levels of 6.25, 6.25,and 5.88at.%,respectively.The defect concentration could be reduced using a larger supercell for the real systems;however,this study was lim-ited with regard to computer resources.Therefore,the properties of the defects calculated from a 2Â2Â2ZnO supercell such as this could be used as qualitative analysis.1432ZnO BTable 1Formation energy and optimized structure of BZO with varying intrinsic defects.Formation energy (eV)Optimized structure O-richO-poor Zn–O (Å)B–O (Å)4V (%)ZnO –– 1.981––B Zn3.750.39 1.996 1.526À3.1B Zn V Zn 5.68 5.81 1.993 1.530À3.3B Zn V O 7.550.70 1.995 1.521À5.3B Zn Zn i10.513.662.0031.5174.74.5 eV2.15 eV3.25 eV4.68 eV4.41 eV(a)(b)(c)(d)Band structures of B-doped ZnO for (a)B Zn ,(b)B Zn V Zn ,(c)B Zn V O models.Y.-C.Peng et al./Optical Materials 39(2015)34–3935All models presented in this study were developed using CASTEP software [18].Structural optimization was performed on each model before calculating properties.The Monkhorst–Pack scheme [19]K-points grid sampling in the supercells was set at 4Â4Â2.Electron–ion interactions were modeled using the ultrasoft pseudo-potential method [20].The valence configurations of the atoms were 4s 23d 10for Zn,2s 22p 4for O,and 2s 22p 1for B.The elec-tron wave functions were expanded in plane wave with an energy cutoff of 380eV.In the structural optimization process,the change in energy,maximum force,maximum stress,and maximum displacement tolerances were set at 10À5eV/atom,0.03eV/Å,0.05GPa,and 0.001Å,respectively.The energy convergence crite-rion for the self-consistent field was set at 10À6eV.To describe the electronic structures more accurately,we adopted the DFT +U d +U p method [21],in which the U d value for Zn-3d and the U p value for O-2p orbitals were set at 10and 7eV,respectively.The band structures,band gaps,and Zn-3d orbital locations of pure ZnO,which were used for the selection of U d and U p values,can be referenced in our previous research [17,22].3.Results and discussion 3.1.Optimized structureThe average bond lengths and volume difference ratio,as obtained from geometric optimization,are summarized in Table 1.In pure ZnO,each Zn atom is bonded to its three horizontal and one vertical oxygen neighbors.The average bond length of Zn-O is 1.981Åand optimized lattice constants are a =b =3.249Åandc =5.232Å,which are in agreement with the experimental values of a =b =3.249,c =5.206Å[23].Following the substitution of one B atom for one Zn atom (B Zn model),the Zn–O bond length is longer than that of B–O (1.526Å).This is because the B 3+radius (0.27Å)is smaller than that of Zn 2+(0.74Å)[24].Therefore,the cell volume of B Zn model shrinks,which is consistent with the experi-mental results [25].Clearly,the presence of Zn or O vacancies in BZO also leads to a shrinkage in volume.Conversely,the presence of interstitial Zn leads to a longer Zn–O length and expansion in volume.3.2.Formation energyTo examine the relative stability of BZO with intrinsic defects in neutral charge state,the defect formation energy can be expressed as follows:[26,27]E f ðD Þ¼E tot ðD ÞÀE tot ðZnO ÞþXn i l ið1Þwhere E tot (ZnO)and E tot (D )are the total energy in pure ZnO and in the defective systems,respectively.n i is the number of i atoms removed from or added to the supercell.If an atom is removed from the supercell,n i is positive,otherwise is negative.l i is the chemical potential of atom i .Formation energy depends on the growth envi-ronment during the preparation process,which can be O-rich or O-poor (Zn-rich).In thermo-dynamic equilibrium,D l Zn +D l O =D H f (ZnO),where D H f (ZnO)represents the formation enthalpy of ZnO.For the chemical potential of B,this study adopted the relation of 2D l B +3D l O 6D H f (B 2O 3)under O-rich conditions and l B =l B(bulk)under O-poor conditions,where D H f (B 2O 3)represents the(a)(b)(c)(d)V ZnV OZn iBZnOO density difference for (a)B Zn ,(b)B Zn V Zn ,(c)B Zn V O ,and (d)B Zn Zn i models.The red,orange,yellow,green,and interpretation of the references to color in this figure legend,the reader is referred to the web version 36Y.-C.Peng et al./Optical Materials 39(2015)34–39formation enthalpy of B2O3.D l i represents the chemical potential of atom i referred to as the elemental solid/gas of l i(bulk/molecule).It is well known that a defective structure with lower formation energy forms more readily and denotes an increased occurrence of defects.Table1presents a summary of the calculated formation energy of BZO with various intrinsic defects,based on the neutral charge state.With the existence of B Zn,E f(B Zn V Zn)<E f(B Zn V O)<E f (B Zn Zn i)under O-rich conditions,implying that O-rich conditions are more likely to induce the formation of V Zn,followed by V O and Zn i.Under O-poor conditions,E f(B Zn V O)<E f(B Zn Zn i)<E f (B Zn V Zn),which implies that O-poor conditions are more likely to induce the formation of V O.As a result,process conditions,such as O2gasflow rate and substrate temperature,largely determine the type of intrinsic defects that form in BZO during preparation. The occurrence of V O is far more likely under a low-O atmosphere, and V Zn is more likely to occur under a high-O atmosphere.For the sake of comparison,we also calculated the formation energy of a single intrinsic defect(V Zn and V O)in pure ZnO.The calculated values of E f(V Zn)and E f(V O)are3.09and4.33eV under O-rich conditions and6.58and0.84eV under O-poor conditions. Thus,we can see that the formation energy of a Zn vacancy from pure ZnO(E f(V Zn))is greater than that obtained from BZO(E f(B Zn V Zn)ÀE f(B Zn)=1.93eV under O-rich conditions and5.42eV under O-poor conditions).This demonstrates that Zn vacancies form more easily in BZO than in ZnO.These results are similar to those calculated for O vacancies,which implies that B-doping facilitates the formation of V Zn and V O.Previous studies [12]obtained similar results,indicating that a greater number of oxygen vacancies or defects exist in BZO than in pure ZnO.3.3.Electronic structureTo clarify the influence of intrinsic defects on the electronic structure of BZO,we calculated the band structure,difference in charge density,and density of states(DOS),as shown in Figs.2–4,respectively.In our previous study[17,22],the calculated band structure revealed a band gap of3.37eV in pure ZnO,which is in excellent agreement with values obtained in experiments.In the present study,we focus on the properties of BZO with intrinsic defects.Fig.2presents the band structures for BZO with various intrin-sic defect models.The Fermi level indicated by the dotted line was set to zero.Fig.2(a)shows the situation in which a Zn atom in pure ZnO is replaced by a B atom,in which the Fermi level shifts from the valence band(VB)maximum to the bottom of the conduction band(CB),resulting in a shallow donor level at the bottom of the CB.The shallow donor level at B doping causes an increase in the optical band gap to4.5eV at B concentration of6.25at.%,which is well known as the Burstein-Moss effect[28].The definitionof Fig.4.Density of states for(a)B Zn,(b)B Zn V Zn,(c)B Zn V O,and(d)B Zn Zn i models.optical band gap is from the top offor n-type semiconducting materials and the bottom of conduction band for materials.Similar tendencies were experiment-based studies[29,30].Asin the vicinity of B impurities appears atoms.The calculated Mulliken bond and B–O bonds are0.371and0.658, that a B–O bond is more covalent than Mulliken bond population represents characteristics).As shown in Fig.4(a),to the bottom of CB are the Zn-4s anda few O-2s and O-2p orbitals.The main extra electron tofill up the CBM.According to the results calculated regarded as an intrinsic defect under the B Zn V Zn model(Fig.2(b)),when donor levels coexist,the empty states produced trons from the B Zn donor level,resulting level as well as the formation of p-type band gap of B Zn V Zn can be narrowed to eration of conduction electrons requires energy from the Fermi level to the CB, be required in the B Zn model.Thus,in may lead to a decrease in the carrier known that mobility is related to the time.The relaxation time could not be software and was assumed as a defects in BZO.The followingeffects of the effective mass on thenear the Fermi level appear nearlyof carriers with a smaller curvature The larger effective mass is related toTherefore,V Zn defects in BZO reduce both carrier concentration as well as mobility,which consequently increases the resistivity of BZO.Fig.3(b)shows that the O atoms surrounding a Zn vacancy gain fewer electrons(green color),implying the occurrence of a number of empty states of O atoms.These empty states are O-2p orbitals near the Fermi level,as shown in Fig.4(b).V O and Zn i can be regarded as intrinsic defects in an O-poor environment.Fig.2(c)and(d)show the band structures in B Zn V O and B Zn Zn i models,in which n-type conductive characteristics appear and the optical band gap increases to4.68eV and4.41eV, respectively.One shallow donor state and one deep donor state occur in these two models.In the B Zn V O model,the deep donor level is probably the charge remaining in the oxygen vacancy (Fig.3(c));in the B Zn Zn i model,it is probably the covalence charge in the vicinity of the interstitial Zn atom(Zn i)(Fig.3(d)).Fig.4(c) and(d)show that the shallow donor level in both models origi-nated from B doping,whereas the deep donor level in the B Zn V O and B Zn Zn i models originated from the addition of V O and Zn i, respectively.The deep donor level in the B Zn V O model comprises mainly Zn and O atoms;however,in the B Zn Zn i model,it also includes B atom(B-2s and B-2p states).The shallow donor states provide conduction electrons;however,the deep donor states may contribute less to the increase in carrier concentration.Qual-itatively,the curvature of the energy band near the Fermi level in the B Zn Zn i model is smaller than that in the B Zn V O model.There-fore,Zn i defects present in BZO increase the effective mass,which may consequently decrease the mobility and conductivity of BZO.3.4.Optical propertiesThe optical properties can be described via the dielectric func-tion e(x)=e1(x)+i e2(x)[31].The imaginary part of the dielectric function e2(x)is calculated as follows:e2¼2e2pX e0Xk;v;cu ckuÁrj j u v k2d E ckÀE vkÀxÀÁð2Þwhere e is the electronic charge;X is the unit cell volume;u is the vector defining the polarization of the incident electricfield;x is the frequency of light;and u c k and u v k are the wave functions of the conduction and valence bands,respectively.Fig.5(a)shows the e2(x)of BZO with various intrinsic defects. In the B Zn model,a blue-shift in the intrinsic absorption edge occurred due to an enlarged optical band gap as compared with ZnO.The shallow donor levels mentioned in Section3.3resulted in an absorption peak at1.2eV.The absorption peaks in the intrin-sic defect models were as follows:B Zn V Zn(0.3eV),B Zn V O(1.5eV), and B Zn Zn i(0.9eV).These peaks resulted in enhanced absorption in the visible range.The peak of B Zn V Zn is the lowest,which can probably be attributed to the transition between occupied states and unoccupied states near the Fermi level.In the B Zn V O,and B Zn Zn i models,the absorption in the visible range may be the result of a shift from the shallow and deep donor occupied states to the unoccupied states of the conduction band.Fig.5(b)presents the transmittance of BZO under various defec-tive models.Table2presents the calculated values for average transmittance associated with each model under UV and visible light.It is should be noted that the calculated results were based on the doping levels of B(6.25at.%),V Zn(6.25at.%)V O(6.25at.%), and Zn i(5.88at.%).The average transmittance of pure ZnO is89.2 %in the visible region and65.6%in the UV region.Fig.5(b)shows that the incorporation of B into ZnO decreased transmittance in the range of800–1200nm(infrared region)and400–800nm(visible light region),but increased transmittance in the range of200–400nm(UV region),compared with pure ZnO.When V Zn was introduced to BZO,transmittance in the visible light region was Optical properties of BZO with varying intrinsic defects.(a)Imaginary dielectric function,(b)Transmittance.38increased,but transmittance in the UV region decreased,compared with BZO.When V O or Zn i was introduced to BZO,the transmit-tance of visible as well as UV light declined significantly,which implies that transmittance could be reduced by employing a low-O environment for fabrication.This may explain why trans-mittance is enhanced by an increase in oxygen pressure during processing[7].4.ConclusionsThis study used the DFT+U method to investigate the influence of intrinsic defects on the formation energy,crystal structure,elec-tronic structure,and optical properties of BZO.Our results revealed that the formation energy of V Zn is lowest under O-rich conditions and the formation energy of V O is lowest under O-poor conditions. V Zn defects in BZO may decrease carrier concentration as well as mobility,which increases transmittance in the visible light region but decreases transmittance in the UV region.V O or Zn i defects in BZO lead to the appearance of n-type conductive characteristics, increasing the optical band gap,and decreasing transmittance in the visible light and UV regions.In addition,Zn i defects increase the effective mass,which may consequently decrease the mobility and conductivity of BZO.Conflict of interestsThe authors declare that there is no conflict of interests regard-ing the publication of this article.AcknowledgementsThis work was supported by the National Science Council in Taiwan(NSC102-2221-E-131-008),for which the authors are grateful.We also acknowledge the National Center for High-performance Computing for computer time and the use of its facilities.Reference[1]T.Minami,Semicond.Sci.Technol.20(2005)S35–S44.[2]L.Zhao,G.Shao,S.Song,X.Qin,S.Han,Rare Metals30(2011)175–182.[3]V.Bhavanasi,C.B.Singh,D.Datta,V.Singh,K.Shahi,S.Kumar,Opt.Mater.35(2013)1352–1359.[4]C.Huang,M.Wang,Z.Deng,Y.Cao,Q.Liu,Z.Huang,Y.Liu,W.Guo,Q.Huang,J.Mater.Sci.–Mater.Electron21(2010)1221–1227.[5]J.L.Zhao,X.W.Sun,H.Ryu,Y.B.Moon,Opt.Mater.33(2011)768–772.[6]L.Cao,L.P.Zhu,W.F.Chen,Z.Z.Ye,Opt.Mater.35(2013)1293–1296.[7]T.Miyata,Y.Honma,T.Minami,J.Vac.Sci.Technol.A25(2007)1193–1197.[8]X.L.Chen,B.H.Xu,J.M.Xue,Y.Zhao,C.C.Wei,J.Sun,Y.Wang,X.D.Zhang,X.H.Geng,Thin Solid Films515(2007)3753–3759.[9]D.W.Kang,J.Y.Kwon,D.J.Lee,M.K.Han,J.Electrochem.Soc.159(2012)H61–H65.[10]C.David,T.Girardeau, F.Paumier, D.Eyidi, croix,N.Papathanasiou,B.P.Tinkham,P.Gu´erin,M.Marteau,J.Phys.:Condens.Matter23(2011)334209.[11]H.Yang,X.Xu,X.Zhou,Y.Ma,J.Dong,T.Wang,J.Miao,Y.Jiang,J.Mater.Sci.47(2012)6513–6516.[12]A.B.Patil,K.R.Patil,S.K.Pardeshi,J.Solid State Chem.184(2011)3273–3279.[13]S.Yılmaz,J.Nisar,Y.Atasoy,E.McGlynn,R.Ahuja,M.Parlak,E.Bacaksız,Ceram.Int.39(2013)4609–4617.[14]L.Li,W.Wang,H.Liu,X.Liu,Q.Song,S.Ren,J.Phys.Chem.C113(2009)8460–8464.[15]X.Qu,W.Wang,S.Lv,D.Jia,Solid State Commun.151(2011)332–336.[16]G.Ji,Z.Gu,M.Lu,J.Zhou,S.Zhang,Y.Chen,Physica B405(2010)4948–4950.[17]H.C.Wu,Y.C.Peng,C.C.Chen,Opt.Mater.35(2013)509–515.[18]M.D.Segall,P.J.D.Lindan,M.J.Probert,C.J.Pickard,P.J.Hasnip,S.J.Clark,M.C.Payne,J.Phys.:Condens.Matter.14(2002)2717–2744.[19]H.J.Monkhorst,J.D.Pack,Phys.Rev.B13(1976)5188–5192.[20]D.Vanderbilt,Phys.Rev.B41(1990)7892–7895.[21]X.Ma,B.Lu,D.Li,R.Shi,C.Pan,Y.Zhu,J.Phys.Chem.C115(2011)4680–4687.[22]H.C.Wu,Y.C.Peng,T.P.Shen,Materials5(2012)2088–2100.[23]R.D.Vispute,V.Talyansky,S.Choopun,R.P.Sharma,T.Venkatesan,Appl.Phys.Lett.73(1998)348–350.[24]D.R.Lide,CRC Handbook of Chemistry and Physics,87th ed.,Taylor andFrancis,Philadelphia,2006.[25]X.G.Xu,H.L.Yang,Y.Wu,D.L.Zhang,S.Z.Wu,Appl.Phys.Lett.97(2010)232502.[26]A.Janotti, C.G.Van de Walle,Phys.Rev.B:Condens.Matter.76(2007)165202.[27]T.Guo,G.Dong,Q.Chen,X.Diao,F.Gao,J.Phys.Chem.Solids75(2014)42–47.[28]P.V.Kamat,N.M.Dimitrijevic, A.J.Nozik,J.Phys.Chem.93(1989)2873–2875.[29]L.Gao,Y.Zhang,J.M.Zhang,K.W.Xu,Appl.Surf.Sci.257(2011)2498–2502.[30]B.N.Pawar,S.R.Jadkar,M.G.Takwale,J.Phys.Chem.Solids66(2005)1779–1782.[31]R.Chowdhury,S.Adhikari,P.Rees,Physica B405(2010)4763–4767.Table2Average transmittance of BZO with varying intrinsic defects.UV region(%)Visible region(%)ZnO65.689.2B Zn91.175.6B Zn V Zn68.186.8B Zn V O52.053.2B Zn Zn i59.256.9Y.-C.Peng et al./Optical Materials39(2015)34–3939。

Optical evidence of strong coupling between valence-band holes and d-localized spinsin Zn1−x Mn x OV.I.Sokolov,1A.V.Druzhinin,1N.B.Gruzdev,1A.Dejneka,2O.Churpita,2Z.Hubicka,2L.Jastrabik,2and V.Trepakov2,3 1Institute of Metal Physics,UD RAS,S.Kovalevskaya Str.18,620041Yekaterinburg,Russia2Institute of Physics,AS CR,v.v.i.,Na Slovance2,18221Praha8,Czech Republic3Ioffe Institute,RAS,194021St-Petersburg,Russia͑Received3December2009;revised manuscript received2March2010;published30April2010͒We report on optical-absorption study of Zn1−x Mn x O͑x=0–0.06͒films on fused silica substrates takingspecial attention to the spectral range of the fundamental absorption edge͑3.1–4eV͒.Well-pronounced exci-tonic lines observed in the region3.40–3.45eV were found to shift to higher energies with increasing Mnconcentration.The optical band-gap energy increases with x too,reliably evidencing strong coupling betweenoxygen holes and localized spins of manganese ions.In the3.1–3.3eV region the optical-absorption curve inthe manganese-containedfilms was found to shift to lower energies with respect to that for undoped ZnO.Theadditional absorption observed in this range is interpreted as a result of splitting of a localized Zhang-Rice-typestate into the band gap.DOI:10.1103/PhysRevB.81.153104PACS number͑s͒:78.20.ϪeI.INTRODUCTIONDilute magnetic semiconductor Zn1−x Mn x O is one of themost promising materials for the development of optoelec-tronic and spin electronic devices with ferromagnetism re-tained at practical temperatures͑i.e.,Ͼ300K͒.However,researchers are confronted with many complex problems.Ferromagnetic ordering does not always appear and the na-ture of its instability is a subject of controversy.In addition,optical properties of Zn1−x Mn x O appreciably differ fromthose in Zn1−x Mn x Se and Zn1−x Mn x S related compounds,where the intracenter optical transitions of Mn2+ions areconventionally observed in the optical-absorption and photo-luminescence spectra.1,2In contrast,a very intense absorp-tion in the2.2–3.0eV region was reported in Zn1−x Mn x Owithout any manifestations of intracenter transitions,3–5and photoluminescence due to4T1→6A1optical transition of Mn2+is absent as well.Interpretation of this absorption bandas a charge transfer3,5is complicated by the fact that Mn2+forms neither d5/d4donor nor d5/d6acceptor levels in the forbidden gap of ZnO.6,7To resolve this contradiction,Dietl8put forward the con-cept that the oxides and nitrides belong to the little studiedfamily of dilute magnetic semiconductors with strong corre-lations.Characteristic features of such compounds are an in-crease in the band gap with the concentration of magneticions and emergence of a Zhang-Rice͑Z-R͒-type state in theforbidden gap9arising as a result of strong exchange cou-pling of3d-localized spin of the impurity centers andvalence-band holes.According to Ref.8,fulfillment ofstrong hybridization condition depends on the ratio of theimpurity-center potential U to a critical value U c;a coupledhybrid state can be formed when U/U cϾ1.Existence of such electronic state has been verified by ab initio theoretical treatment of electron correlations using the local spin-density approximation͑LSDA+U model͒and calculation of the ex-change coupling values.10In Zn1−x Mn x O the hole can origi-nate by electron transfer from the Mn2+adjacent oxygen to the conduction band.The resulting hole localizes as the Z-R state leading to appearance of additional broad,intense ab-sorption band.In this way the study of optical-absorptionspectra can be used as a probe to identify the Z-R states.It is known that the optical band-edge absorption spec-trum of Mn-doped ZnO is characterized by the onset of astrong rise of the absorption coefficient in theϳ3.1eV spec-tral region.11In Refs.11and12,this absorption inZn1−x Mn x Ofilms was treated as a product of direct interbandoptical transitions using conventional formula␣2ϳ͑ប␻−E g͒.The resulting magnitudes of band gap for composition with x=0.05have been estimated as E g=3.10eV͑Ref.11͒and3.25eV,12which is appreciably less than E g=3.37eV inZnO.13Such“redshift”of the band gap was considered inRef.12as a result of p-d exchange interaction,in analogy tothe shift of the excitonic lines in reflectivity and lumines-cence spectra observed in Ref.14for Zn1−x Mn x Se.At thesame time theory predicts an increase in E g͑x͒with x for Zn1−x Mn x O.8Also excitonic absorption spectrum in Zn1−x Mn x O nanopowders,15appeared to be located at ener-gies higher than that in ZnO nanopowders,that does not confirm the shift of E g to lower energies for Zn1−x Mn x O films.In this work we report on the optical-absorption spectrastudies in thin Zn1−x Mn x Ofilms deposited on fused silicaing suchfilms we succeed to detect the absorp-tion spectra of excitons and to determine reliably the widthof the optical gap E g.This allowed us to elucidate the natureof the additional absorption band appearing atប␻ϽE g near the fundamental absorption edge as a result of splitting of one more Z-R-type state due to strong hybridization and ex-change coupling of3d-localized spin of the manganese and valence-band oxygen hole.II.EXPERIMENTALThin Zn1−x Mn x Ofilms with x=0–0.06,120–130,and 200–250nm of thicknesses were deposited on fused silica substrates by the atmospheric barrier-torch discharge tech-nique,as it was described in Refs.16and17.The substratePHYSICAL REVIEW B81,153104͑2010͒temperature during deposition was kept at ϳ200°C.Mn content was controlled by measurements of Mn and Zn emis-sion ͑␭em =4031Åand 4810Å,respectively ͒of plasma during deposition and crosschecked by the postgown EPMA ͑JEOL JXA-733device with Kevex Delta Class V mi-croanalyser ͒analysis with accuracy Ϯ0.3%.X-ray diffrac-tion ͑XRD ͒studies were performed with a Panalytical X’PertMRD Pro diffractometer with Eulerian cradle using Cu K ␣radiation ͑␭em =1.5405Å͒in the parallel beam ge-ometry.XRD profiles were fitted with the Pearson VII func-tion by the DIFPATAN code.18Correction for instrumental broadening was performed using NIST LaB6standard and V oigt function method.19Optical absorption within the 1.2–6.5eV spectral region was measured in unpolarized light at room temperature using a Shimadzu UV-2401PC spectrophotometer.The bare silica substrate and Zn 1−x Mn x O film on silica substrate were mounted into the reference and test channel,respectively.The optical density ␣d ͑product of optical-absorption coeffi-cient and film thickness ͒was calculated without taking into account multiple reflections as ␣d =ln ͑I 0/I ͒,where I 0and I are intensities of light passed through bare substrate and film/substrate structure.III.RESULTS AND DISCUSSIONFigure 1presents XRD pattern for ZnO and Zn 0.95Mn 0.05O films,as an example.All obtained films re-vealed crystalline block structure with dominant ͑002͒orien-tation of blocks’optical C -axes aligned normal to substrate.Observed reflexes correspond to wurtzite structure evi-dencing absence of extraneous phases.Both pure and Mn-doped ZnO films appeared to be compressively strained with 0.2%of strain,s =͑a 0−a S ͒/a 0,where a 0and a S are the lattice parameters of nonstrained and strained films.The analysis reveals that the value of compressive strain is controlled pre-dominantly by stresses,but not by presence of Mn ͑at least for Mn concentrations used ͒.Figure 2presents the optical-absorption spectra for Zn 1−x Mn x O films.A wide absorption line is seen in the re-gion of the band edge ͑Fig.2͒,whose energy appears to be shifted by about 100meV to higher energies in comparison with the excitonic line in ZnO ͓ϳ3.31eV at T =300K ͑Ref.13͔͒.The line shift is very likely connected with the com-pressive strain of Zn 1−x Mn x O films mentioned above.The wide and shifted line has been observed earlier in ZnO film on sapphire substrate 20,21and was identified as a shift of the excitonic line due to compressive strain of Zn 1−x Mn x O films.21The inset represents spectra of this line obtained in ZnO at T =300K and 77.3K.It is seen that the excitonic line is narrowed,split into two components and shifted to higher energies on lowering the temperature,clearly evidenc-ing its excitonic nature.The first line is a sum of A and B excitons,the second one is the C exciton appearing due to disorientation of blocks forming the film.16Analogous tem-perature evolutions have been reported for a wide excitonic line in ZnO nanocrystals.15As the concentration of Mn impurity increases,the exci-tonic line additionally broadens and shifts to higher energies.Figure 3shows the actual Mn concentration shift of the ex-citonic line energy ប␻exc .It is seen that the increase in Mn concentration leads to not only changes in the excitonic spec-trum but also exhibits enhancement of the band-gap energy in Zn 1−x Mn x O films ͑band-gap magnitude can be estimated as E g =ប␻exc +E exc ,where E exc =60meV is the excitonic binding energy 13͒.It is known that the band-gap magnitude in ZnO-MnO system varies from 3.37eV in ZnO up to 3.8eV in MnO.22According to the theoretical analysis 8per-formed taking into account inversion of ⌫7and ⌫9valence subbands in ZnO,23,24strong coupling of manganese spin and p states of valence band leads to appearance of a positiveI n t e n s i t y (c o u n t )2θ(degree)FIG.1.XRD pattern of ZnO ͑left scale ͒and Zn 0.95Mn 0.05O ͑right scale ͒films.E n e r g y (eV)αdFIG.2.Exciton absorption spectra of compressed Zn 1−x Mn x O films:1—x =0%,2—x =1.8%,and 3—x =5%;film thickness:d =͑120–130͒nm;and T =300K.Inset shows excitonic absorption lines for compressed ZnO:1—T =300K and 4—T =77.3K.01234563.403.413.423.433.44E n e r g y (e V )X (%)FIG.3.Mn-concentration dependence of the excitonic line en-ergies for Zn 1−x Mn x O films.additive in optical absorption of Zn 1−x Mn x O at small x val-ues.The sum of two contributions at sufficiently small x results in an increase in E g magnitude.The rise of the band-gap magnitude with the admixture of the second component E g ͑x ͒has been observed in Zn 1−x Co x O ͑Ref.25͒for exci-tonic lines registered in the reflection spectra at 1.6K.The shift of the excitonic line to higher energies was observed in Zn 0.99Fe 0.01O,too.20In the case of weak d -p coupling the additive into the band gap change appeared to be negative.8In this case the band-gap value E g decreases with x for x Յ0.1,as it was found for Zn 1−x Mn x Se ͑Fig.6in Ref.14͒and for Cd 1−x Mn x S.26Therefore,the observed rise of the E g ͑x ͒value with Mn addition provides the reliable experimental proof that the strong hybridization condition U /U c Ͼ1in Zn 1−x Mn x O is fulfilled.Figure 4presents optical absorption in Zn 1−x Mn x O films recorded in the spectral region 3.1–3.3eV .It is seen that the onset of optical absorption in Zn 1−x Mn x O films emerges at lower energies than that for ZnO ones.Analogous shift had been observed earlier in the spectrum of the photoluminescence excitation over deep im-purity centers in Zn 1−x Mn x O for Ref.15.Unlike authors of Refs.11and 12,we assume that addi-tional absorption of Zn 1−x Mn x O ͑in comparison with ZnO ͒in the 3.1–3.3eV range is a result of pushing the Z-R-type states out of valence band to the forbidden gap.9The essence of this state consists of localization of the valence-band hole within the first coordination sphere on the oxygen ions as a result of strong exchange interaction of manganese and hole spins.Such electronic state is similar to the Z-R-type state originally considered for La 2CuO 4oxidesuperconductor.9This state is a singlet one,because in La 2CuO 4the spins of d 9configuration of Cu 2+ion and oxy-gen holes are equal but of opposite direction.The situation is more complex in the case of Zn 1−x Mn x O since the top of valence band is formed by three close subbands:⌫7,⌫9,and ⌫7.23,24In such case we have serious reasons to assume that not only the presence of one deep Z-R-type state is respon-sible for optical absorption in the 2.2–3.0eV spectral region.We assume the presence of another,relatively shallow Z-R-type state too,which has been split off into the gap providing additional absorption in the 3.1–3.3eV region of Zn 1−x Mn x O.Tentatively,using results 11,12,15we estimate the splitting of the second Z-R level from the valence band as 0.12–0.27eV .More reliable determination of the split energy can be performed using more sensitive methods of absorp-tion spectra, e.g.,modulation methods,which are in progress.IV .CONCLUSIONThin Zn 1−x Mn x O films ͑x =0–0.06͒have been sintered and their optical-absorption spectra were investigated.The well-pronounced excitonic absorption lines in the fundamen-tal absorption spectral regions were observed.Position of excitonic absorption lines in Zn 1−x Mn x O films shifts to higher energies with increasing Mn content.This evidences an increase in the E g magnitude with x for small values x and reliably corroborates fulfillment of the strong coupling crite-rion ͑U /U c Ͼ1͒in Zn 1−x Mn x O.The last effect leads to emer-gence of an intense optical-absorption band in the 2.2–3.0eV region due to the presence of the band-gap Z-R-type state.The additional absorption observed in the range of 3.1–3.3eV is interpreted as a result of splitting of one more Z-R-type states into the band gap.ACKNOWLEDGMENTSAuthors thank T.Dietl,V .I.Anisimov,and A.V .Lukoy-anov for useful discussions and V .Valvoda for kind assis-tance in XRD experiments.This work was supported by Czech Grants No.A V0Z10100522of A V CR,No.KJB100100703of GA A V ,No.202/09/J017of GA CR,No.KAN301370701of A V CR,and No.1M06002of MSMT CR and Russian Grants No.08-02-99080r-ofiof RFBR,PP RAS “Quantum Physics of Condensed Matter”,and State Contract No.5162.nger and H.J.Richter,Phys.Rev.146,554͑1966͒.2T.Hoshina and H.Kawai,Jpn.J.Appl.Phys.19,267͑1980͒.3F.W.Kleinlein and R.Helbig,Z.Phys.266,201͑1974͒.4R.Beaulac,P.I.Archer,and D.R.Gamelin,J.Solid State Chem.181,1582͑2008͒.5T.Fukumura,Z.Jin,A.Ohtomo,H.Koinuma,and M.Kawasaki,Appl.Phys.Lett.75,3366͑1999͒.6K.A.Kikoin and V .N.Fleurov,Transition Metal Impurities in Semiconductors:Electronic Structure and Physical Properties ͑World Scientific,Singapore,1994͒,p.349.7T.Dietl,J.Magn.Magn.Mater.272-276,1969͑2004͒.8T.Dietl,Phys.Rev.B 77,085208͑2008͒.9F.C.Zhang and T.M.Rice,Phys.Rev.B 37,3759͑1988͒.10T.Chanier,F.Virot,and R.Hayn,Phys.Rev.B 79,205204͑2009͒.11V .Shinde,T.Gujar,C.Lokhande,R.Mane,and S.-H.Han,3.1253.2500.00.40.8αdEnergy (eV)12FIG.4.Spectral dependence of the optical density ␣d in the 3.1–3.3eV spectral region for Zn 1−x Mn x O,1—ZnO;2—x =0.3–0.5%;film thickness 200–250nm;and T =300K.Mater.Chem.Phys.96,326͑2006͒.12Y.Guo,X.Cao,n,C.Zhao,X.Hue,and Y.Song,J.Phys. Chem.C112,8832͑2008͒.13Zh.L.Wang,J.Phys.:Condens.Matter16,R829͑2004͒.14R.B.Bylsma,W.M.Becker,J.Kossut,U.Debska,and D. Yoder-Short,Phys.Rev.B33,8207͑1986͒.15V.I.Sokolov,A.Ye.Yermakov,M.A.Uimin,A.A.Mysik,V.A.Pustovarov,M.V.Chukichev,and N.B.Gruzdev,J.Lumin.129,1771͑2009͒.16M.Chichina,Z.Hubichka,O.Churpita,and M.Tichy,Plasma Processes Polym.2,501͑2005͒.17Z.Hubicka,M.Cada,M.Sicha,A.Churpita,P.Pokorny,L. Soukup,and L.Jastrabík,Plasma Sources Sci.Technol.11,195͑2002͒.18http://www.xray.cz/priv/kuzel/dofplatan/19R.Kuzel,Jr.,R.Cerny,V.Valvoda,and M.Blomberg,ThinSolid Films247,64͑1994͒.20Z.Jin,T.Fukumura,M.Kaasaki,K.Ando,H.Saito,T.Skiguchi, Y.Z.Yoo,M.Murakami,Y.Matsumoto,T.Hasegawa,and H. Koinuma,Appl.Phys.Lett.78,3824͑2001͒.21J.-M.Chauveau,J.Vives,J.Zuniga-Perez,ügt,M.Teis-seire,C.Deparis,C.Morhain,and B.Vinter,Appl.Phys.Lett.93,231911͑2008͒.d and V.E.Henrich,Phys.Rev.B38,10860͑1988͒. 23K.Shindo,A.Morita,and H.Kamimura,J.Phys.Soc.Jpn.20, 2054͑1965͒.24W.Y.Liang and A.D.Yoffe,Phys.Rev.Lett.20,59͑1968͒. 25W.Pacuski,D.Ferrand,J.Gibert,C.Deparis,J.A.Gaj,P.Ko-ssacki,and C.Morhain,Phys.Rev.B73,035214͑2006͒.26M.Ikeda,K.Itoh,and H.Sato,J.Phys.Soc.Jpn.25,455͑1968͒.。

玻璃纤维织物表面Ni-P合金涂层的制备及其导电性能研究秦文峰;郭荣辉;梁科;唐庆如【摘要】采用化学镀的方法在玻璃纤维织物试样表面制备了Ni-P合金沉积的非晶镀层.利用扫描电子显微镜和X射线观察及分析了镀层的表面形貌与表面结构,研究了硫酸镍的浓度对非晶镀层的沉积速率、沉积量以及导电性能的影响.结果表明,随着硫酸镍浓度的增加,沉积速率和沉积量逐渐升高,而镀层方阻值逐渐降低,导电性增加.当硫酸镍浓度20 g/L时,玻璃纤维织物镀层方阻值为1.35方,具有良好的导电性.【期刊名称】《科学技术与工程》【年(卷),期】2015(015)035【总页数】4页(P149-152)【关键词】玻璃纤维;化学镀;Ni-P合金;无钯活化;导电性【作者】秦文峰;郭荣辉;梁科;唐庆如【作者单位】中国民航飞行学院航空工程学院,广汉618307;四川大学轻纺与食品学院,成都610065;中国民航飞行学院航空工程学院,广汉618307;中国民航飞行学院航空工程学院,广汉618307【正文语种】中文【中图分类】TG153.1玻璃纤维具有耐高温、抗化学腐蚀、强度高、模量高等一系列优良性能，作为树脂基复合材料重要的增强材料，已在航空、航天、舰船、化工冶金等领域得到了充分应用[1—3]。

通过现代化学物理方法改性玻璃纤维，赋予玻璃纤维新的功能，如导电、色彩、发光、传感等，可以进一步拓展玻璃纤维的应用领域[4—8]。

导电玻璃纤维是通过物理或化学的方法在玻璃纤维表面涂覆一层导电层，使其具有优异的导电性，在屏蔽材料、电热材料、隐身材料等方面具有潜在的应用[9—11]。

碳纤维增强复合材料由于具有高的比强度、比刚度和抗疲劳性能在飞机上应用越来越广泛，然而其差的导电性能更容易遭受雷击损失，导电玻璃纤维常铺覆在碳纤维增强复合材料结构表面以抗雷击。

通常导电玻璃纤维可通过纤维中混入抗静电剂使纤维表面具有离子性而提高其导电性，或对纤维表面改性镀上一层导电金属涂层，以提高导电率。

CHINESE JOURNAL OF CHEMICAL PHYSICS JANUARY25,2016ARTICLECrystallization Behavior and Properties of B-Doped ZnO Thin Films Prepared by Sol-Gel Method with Different Pyrolysis Temperatures Bin Wen a,Chao-qian Liu a∗,Nan Wang a,Hua-lin Wang a,Shi-min Liu a,Wei-wei Jiang a,Wan-yu Ding a,Wei-dong Fei b,c∗,Wei-ping Chai aa.Engineering Research Center of Optoelectronic Materials&Devices,School of Materials Science andEngineering,Dalian Jiaotong University,Dalian116028,Chinab.School of Materials Science and Engineering,Harbin Institute of Technology,Harbin150001,Chinac.School of Mechanical Engineering,Qinghai University,Xining810016,China(Dated:Received on June11,2015;Accepted on August14,2015)Boron-doped zinc oxide transparent(BZO)films were prepared by sol-gel method.The effectof pyrolysis temperature on the crystallization behavior and properties was systematicallyinvestigated.XRD patterns revealed that the BZOfilms had wurtzite structure with apreferential growth orientation along the c-axis.With the increase of pyrolysis temperature,the particle size and surface roughness of the BZOfilms increased,suggesting that pyrolysistemperature is the critical factor for determining the crystallization behavior of the BZOfilms.Moreover,the carrier concentration and the carrier mobility increased with increasingthe pyrolysis temperature,and the mean transmittance for everyfilm is over90%in thevisible range.Key words:Transparent conduction oxide,Thinfilm,Boron-doped ZnO,Pyrolysis tem-perature,Sol-gelI.INTRODUCTIONZinc oxide(ZnO)is a direct wide band gap semicon-ductor with E g=3.37eV,and is naturally an n-type semiconductor due to oxygen vacancies and interstitial zinc atoms.In addition,ZnO is abundant,nontoxic, and stable in reducing atmosphere.It is considered as a promising candidate to replace indium tin oxide as transparent conducting electrodes in solar cell devices andflat panel display[1−3].To enhance the electri-cal properties of ZnO,various atoms(e.g.Al,In,Ga, B,F)have been employed as donors[4−7].Wherein, boron-doped ZnO has not only high transparency over the visible and near-infrared range,and low electrical resistivity,but also excellent light scattering property [8,9].Therefore,B-doped ZnO thinfilm has attracted some attention in recent years.Generally,B-doped zinc oxide(BZO)thinfilms were primarily synthesized by chemical vapor deposition [10−15]and spray pyrolysis[16,17].Also,there are a few studies on the BZO thinfilms deposited by sol-gel method[18−23].The sol-gel process has many advan-tages in preparing thinfilms,including low cost,excel-lent compositional control,easy handling and feasibility of deposition on large-area substrate[24].In previous studies on the BZOfilms prepared by sol-gel process,∗Authors to whom correspondence should be addressed.E-mail: cqliu@,wdfei@ the effects of annealing temperature[18],doping con-centration of boron[19−23],and pH of precursor sol [1]on the crystallization,microstructure,electrical and optical properties of BZOfilms were reported system-atically.To the best of our knowledge,the effect of py-rolysis temperature on the properties of BZOfilm has not been reported.In this work,BZOfilms were pre-pared by sol-gel spin coating and pyrolyzed at different temperatures,and the dependence of the properties of the BZOfilms on the pyrolysis temperatures was inves-tigated.II.EXPERIMENTSBoron-doped ZnO precursor solution was prepared from zinc acetate di-hydrate(Zn(Ac)2·2H2O,AR)and boric acid(H3BO3,GR)as sources for Zn and B,where the B/Zn atomic ratio wasfixed at0.5at.%.The de-tailed solution preparation was described in our previ-ous work[23].Thefilms were prepared by spin-coating the solution onto cleaned quartz glass substrates under 2000r/min for10s atfirst.Then,each layer was di-rectly put into a homemade tube furnace at350−500◦C for2min to evaporate the solvent and pyrolyze organ-ics,where the heating time from room temperature to pyrolysis temperature was0.5min.The details of the homemade tube furnace were also described in our pre-vious work[25].The spin-coating pyrolyzing procedure was repeated5times for eachfilm.Finally,the de-positedfilms were annealed at500◦C for5min in ArDOI:10.1063/1674-0068/29/cjcp1506116c⃝2016Chinese Physical SocietyChin.J.Chem.Phys.Bin Wen et al. atmosphere.The thickness of all thefilms was about160nm measured by a step profiler(Veeco Dektak6M).The crystal structure of thefilms was analyzed byan X-ray diffractometer(PANalytical Empyrean)withCu Kα1radiation(λ=1.54056˚A)and a G¨o bel mirror at40kV and40mA,where the step size and the count-ing time were0.05◦and0.5s respectively.The surfacemorphologies of the thinfilms were characterized usingan atomic force microscope(AFM,Bruker Multimode8).A Hall effect measurement system(Swing HALL8800)was employed to measure the electrical propertiesof thefilms.Optical transmittance measurements wereperformed by an ultraviolet-visible spectrophotometer(Hitachi U-3310)in the wavelength range from300nmto900nm.III.RESULT AND DISCUSSIONA.StructureThe XRD scan patterns of the BZO thinfilms py-rolyzed at different temperatures are shown in Fig.1(a).It is clear that thefilms exhibit a single-phase hexagonalstructure(wurtzite ZnO JCPDS No.36-1451)and havethe preferred orientation of(002)(i.e.,c-axis preferredorientation).Moreover,the intensity of(002)reflectionwas enhanced with increasing the pyrolysis tempera-ture,suggesting that the pyrolysis temperature is thecritical factor determining the crystallization behaviorof the BZOfilms in the present work.To estimate theaverage grain size of the samples,the Scherers equationis employed:D=0.89λβcosθ(1)where D is the grain size,λis the X-ray wavelength of1.54056˚A,θis Bragg diffraction angle,andβis the full-width at half-maximum(FWHM)of the diffraction peak corresponding to2θ.The FWHM values and cal-culated average grain sizes of thefilms pyrolyzed at dif-ferent temperatures are shown in Fig.1(b).It is clear that the grain size increased with increasing the pyrol-ysis temperature.B.MorphologyIn order to understand deeply the influence of pyrol-ysis temperature on the crystallization behavior of the BZOfilms,the surface morphologies of thefilms were characterized by AFM in contact mode and are shown in Fig.2.From the two-dimensional AFM images,the combined tendency of the particles in thefilms can be clearly observed with increasing pyrolysis temperature. This result also suggests that the pyrolysis temperature is the critical factor for determining the crystallization behavior of the BZOfilms.FIG.1(a)XRD2θscan patterns and(b)FWHM valuesand average crystallite sizes of the BZOfilms deposited atdifferent pyrolysis temperatures.The influence of the pyrolysis temperature on thegrowth behavior of the sol-gel derived BZOfilms canbe understood on the basis of the understanding ofthe pyrolysis process.Primarily,the source material ofZn(Ac)2·2H2O involved in two chemical reaction pro-cesses in the precursor solution[26].Thefirst was areversible hydrolysis reaction:Zn(CH3COO)2·2H2O↔(ZnCH3COO)++CH3COO−+2H++2OH−(2) Then hydrolysis products reacted with mo-noethanolamine in the solvent of2-methoxyethanol through the following chemical reaction:CH3COOZn++CH3COO−+2H++2OH−+NH2CH2CH2OH→Zn(OH)2+CH3COONH2+CH3COOCH2CH3+H2O(3) Evidently,the reaction resultant of Zn(OH)2in the precursor solution is the source of the primary sol par-ticles,and then can form the gel network in the spin-coating processes and can be adsorbed onto the sub-strate to form precursorfilm.According to the previ-ous studies[27,28],it can be known that the organic solvents and reaction resultants in the precursorfilmDOI:10.1063/1674-0068/29/cjcp1506116c⃝2016Chinese Physical SocietyChin.J.Chem.Phys.B-doped ZnO Thin Films(a)(c)(e)(b)(d)(g)(f)(h)0.0 1.0 µm-12.3 nm11.6 nm-20.0 nm12.9 nm13.1 nm16.0 nm-12.3 nm-12.2 nm0.0 1.0 µm0.0 1.0 µm0.0 1.0 µm−0.411.6 0.20.40.60.80.312.9 0.20.40.60.80.20.40.60.80.20.40.60.80.413.1 -0.2 16.0 nm µmµmµmµm0.20.40.60.80.20.40.60.80.20.40.60.80.20.40.60.8nm nm nm FIG.2Two-and three-dimensional AFM images of the BZO films deposited at (a,b)350◦C,(c,d)400◦C,(e,f)450◦C,(g,h)500◦Ccan be entirely evaporated or pyrolyzed at the pyrolysis temperature below 350◦C.Moreover,the decomposi-tion temperatures of Zn(OH)2and H 3BO 3are about 125and 185◦C,respectively.The above discussion in-dicates that there should not be any residual organic component or other volatile matter in the as-pyrolyzed films.Kang et al .[29]considered that the residual or-ganic components in the as-pyrolyzed films would sup-press the crystal growth of the films.Therefore,in our present work,the effect on the particle size in the an-nealed films should be controlled mainly by the pyroly-sis temperature.As for the further understanding about the effect of the pyrolysis temperature on the growth behavior of the sol-gel derived BZO films,it is described as the follow-ing.It is clear that the particle size is very small and less than 20nm in diameter in the film pyrolyzed at 350◦C shown in Fig.2(a).Thus it can be reasonably deduced that the sol particle size in the precursor solu-tion should be smaller than 20nm.As is well known,generally,the smaller the nanoparticle size is,the higher the specific surface energy of the nanoparticle is.There-fore,in the pyrolysis process for preparing the BZO films,the sol particles in the precursor films were easy to merge,and the merging process was susceptible to the pyrolysis temperature.However,the grain growth in the as-pyrolyzed films was difficult in the post anneal-ing process at 500◦C for 5min.Generally,the grain growth due to post annealing corresponds to a recrys-tallization process.When the annealing temperature and time is not high or long enough,the grain growth is difficult.Therefore,although the as-pyrolyzed BZO films were annealed at 500◦C for 5min,the particle size in the films was still mainly controlled by thepyrolysisFIG.3RMS roughness of the BZO films deposited at dif-ferent pyrolysis temperatures.temperature.From that discussed above,we think the pyrolysis temperature is the critical factor affecting the crystallization behavior of the BZO films.The root-mean-square (RMS)roughness of the BZO thin films is shown in Fig.3.It can be seen that the RMS roughness of the thin films increased with increasing py-rolysis ly,the RMS roughness value of the BZO film pyrolyzed at 350◦C was about 2.5nm,and then that of the BZO film pyrolyzed at 500◦C in-creased to about 4.9nm.Evidently,the increase of the RMS roughness originated from the grain growth with increasing pyrolysis temperature.C.Electrical propertiesHall measurements were carried out at room tem-perature to investigate the electrical properties of BZODOI:10.1063/1674-0068/29/cjcp1506116c ⃝2016Chinese Physical SocietyChin.J.Chem.Phys.Bin Wen et al.FIG.4Electrical properties of the BZOfilms as a function of the pyrolysis temperature.films.The resistivity,Hall carrier concentration,and mobility of thefilms as a function of the pyrolysis tem-peratures are presented in Fig.4.When the pyrolysis temperature was raised from350◦C to500◦C,the carrier concentration of the BZOfilms increased from 5.27×1018cm−3to1.77×1019cm−3,and the carrier mo-bility increased from2.04cm2/(V·s)to7.58cm2/(V·s). The increases in the carrier concentration and mobility should be attributed to the crystallization enhancement with increasing pyrolysis temperature.Logically,when the crystalline state of the sample of B-doped ZnO is poor,there will be a large amount of amorphous ZnO and boron oxide in the sample.The crystallization en-hancement means more B atoms were doped into the crystal lattice of ZnO to replace the Zn2+,and then more free charge carrier was released.As a result,the carrier concentration increased with increasing pyroly-sis temperature.Moreover,the crystallization enhance-ment also means the defect concentration in thefilms decreased with increasing pyrolysis temperature.Cor-respondingly,the carrier mobility of the BZOfilms in-creased with increasing pyrolysis temperature.At the pyrolysis temperature of500◦C,the BZOfilm has the lowest resistivity(4.64×10−2Ω·cm)in the present work.D.Optical propertiesThe transmittance spectra(T)of the BZOfilms were measured at room temperature by an ultraviolet-visible spectrophotometer,and are shown in Fig.5(a).All the transmittance spectra show mean values higher than 90%in the visible range.Moreover,it can be observed that the mean transmittances of thefilms in the visi-ble range arefluctuant with pyrolysis temperature.The mean transmittance of thefilm pyrolyzed at350◦C was lower than that of thefilm pyrolyzed at400◦C in the visible range,which may be attributed to the difference in the crystalline states of the twofilms.According to the calculated grain size shown in Fig.1(b)and the two-dimensional AFM images shown in Fig.2,the crystalline state of thefilm pyrolyzed at350◦C was slightly weaker than that of thefilm pyrolyzed at400◦C.Therefore, the defect concentration in the former was higher than that in the latter,and then the mean transmittance of the former was lower than that of the latter in the visible range.When the the pyrolysis temperature ex-ceeded400◦C,the mean transmittance decreased with increasing pyrolysis temperature,which should be due to the increase of carrier concentration with increasing pyrolysis temperature.Generally,the higher the free carrier concentration is,the more serious the free car-rier absorption and reflection in the visible range are. Therefore,according to the Hall measurement results, the mean transmittance of transmittance of thefilms pyrolyzed at higher temperature is lower in the visible range.Generally,boron-doped ZnO is considered as a direct energy gap semiconductor,thus the relationship among absorption coefficient,photon energy,and optical band gap is(αhν)2=A(hν−E g)(4) where A is a constant for a direct transition,hνis pho-ton energy,αis the optical absorption coefficient,and E g is the optical energy gap.To identifyαfor the BZO films,Lambert’s law is used:α=1dln1T(5)where d is thefilm thickness and T is the transmit-tance spectra.The E g was obtained by extrapolating downwards the corresponding straight lines till the in-tersection with energy axis,as shown in Fig.5(b).The determined optical band gaps are shown in the inset of Fig.5(b).The slight blue-shift in optical energy gap is clear with increasing the pyrolysis temperature.The in-crease in optical band gap of the BZO thinfilms should be attributed to Burstein-Moss effect.IV.CONCLUSIONWe have investigated the effect of pyrolysis temper-ature on the crystallization behavior,electrical and optical properties of sol-gel-derived boron-doped ZnO (BZO)films,and found that pyrolysis temperature was a critical factor affecting the crystallization behavior of the sol-gel-derived BZOfilms.XRD patterns revealed that all the BZOfilms had wurtzite structure with a preferential growth orientation along the c-axis.With increasing the pyrolysis temperature,the grain size ofDOI:10.1063/1674-0068/29/cjcp1506116c⃝2016Chinese Physical SocietyChin.J.Chem.Phys.B-doped ZnO Thin FilmsFIG.5(a)Transmittance spectra and(b)(αhν)2versus hνplot of the BZOfilms deposited at different pyrolysis temperatures.Inset:the optical band gap of thefilms.the BZOfilms increased,and the RMS roughness of thefilms also increased.The mean transmittance for everyfilm was over90%in the visible range,and the optical band edge of the BZOfilms exhibited blue shift with increasing pyrolysis temperature.Moreover,with increasing pyrolysis temperature,the carrier concentra-tion and the carrier mobility increased.V.ACKNOWLEDGMENTSThis work was supported by the National Natural Sci-ence Foundation of China(No.51302024,No.51002018 and No.51472039),the Program for Liaoning Excel-lent Talents in University(No.LJQ2012038),the Higher Specialized Research Fund for the Doctoral Program (No.20122124110004),the Project of Education Depart-ment of Liaoning Province(No.L2013179),the Project of Open Research Foundation of State Key Laboratory of Advanced Technology for Float Glass(No.KF1301-01),the Dalian Science and Technology Plan Project (No.2011A15GX025),the Dalian Science and Technol-ogy Plan Project(No.2010J21DW008),and the Qinghai Province Science and Technology Project(No.2012-Z-701).[1]B.Houng, C.L.Huang,and S.Y.Tsai,J.Cryst.Growth307,328(2007).[2]A.Banejee and G.Guha,J.Appl.Phys.69,1030(1991).[3]J.Y.Liu,X.X.Yu,G.H.Zhang,Y.K.Wu,K.Zhang,N.Pan,and X.P.Wang,Chin.J.Chem.Phys.26,225 (2013).[4]Y.S.Kim and W.P.Tai,Appl.Surf.Sci.253,4911(2007).[5]J.C.Wang,F.C.Cheng,Y.T.Liang,H.I.Chen,C.Y.Tsai,C.H.Fang,and T.E.Nee,Nanoscale Res.Lett.7,270(2012).[6]N.A.Estrich,D.H.Hook,A.N.Smith,J.T.Leonard,ughlin,and J.P.Maria,J.Appl.Phys.113,233703(2013).[7]J.Wen,C.Y.Zuo,M.Xu,C.Zhong,and K.Qi,Eur.Phys.J.B80,25(2011).[8]S.Fa¨y,J Steinhauser,N.Oliveira,E.V.Sauvain,andC.Ballif,Thin Solid Films515,8558(2007).[9]X.G.Xu and H.L.Yang,Appl.Phys.Lett.97,232502(2010).[10]G.Kim,J.Bang,Y.Kim,and S.K.Rout,Appl.Phys.A97,821(2009).[11]X.L.Chen,B.H.Xu,J.M.Xue,Y.Zhao,C.C.Wei,J.Sun,Y.Wang,X.D.Zhang,and X.H.Geng,Thin Solid Films515,3753(2007).[12]S.Y.Myong,J.Steinhauser,R.Schluchter,S.Fay,E.V.Sauvain,A.Shah,C.Ballif,and A.Rufenacht,Sol.Energy Mater.Sol.Cells91,1269(2007).[13]J.Hu and R.G.Gordon,J.Electrochem.Soc.139,2014(1992).[14]W.W.Wenas,A.Yamada,and K.Takahashi,J.Appl.Phys.70,7119(1991).[15]W.W.Wenas,A.Yamada,M.Konagai,and K.Taka-hashi,Jpn.J.Appl.Phys.30,L441(1991).[16]B.N.Pawar,S.R.Jadkar,and M.G.Takwale,J.Phys.Chem.Solids66,1779(2005).[17]B.J.Lokhande,P.S.Patil,and M.D.Uplane,PhysicaB302,59(2001).[18]V.Kumar,R.G.Singh,F.Singh,and L.P.Purohit,J.Alloy Compd.544,120(2012).[19]M.Caglara,S.Ilican,Y.Caglar,and F.Yakuphanoglu,pd.509,3177(2011).[20]R.B.H.Tahar and N.B.H.Tahar,J.Mater.Sci.40,5285(2005).[21]S.Jana, A.S.Vuk, A.Mallick, B.Orel,and P.K.Biswas,Mater.Res.Bull.46,2392(2011).[22]V.Kumar,R.G.Singh,L.P.Purohit,and R.M.Mehra,J.Mater.Sci.Technol.27,481(2011).[23]B.Wen,C.Q.Liu,W.D.Fei,H.L.Wang,S.M.Liu,N.Wang,and W.P.Chai,Chem.Res.Chin.Univ.30, 509(2014).[24]H.H.Huang,B.Orler,and G.L.Wilkes,Polym.Bull.14,557(1985).[25]N.Wang,C.Q.Liu,B.Wen,H.L.Wang,S.M.Liu,and W.P.Chai,Mater.Lett.122,269(2014).[26]A. E.Jim´e nez-Gonz´a lez,J. A.Soto Urueta,and R.Su´a rez-Parra,J.Cryst.Growth192,430(1998). [27]S.Ilican,Y.Caglar,and M.Caglar,J.Optoelectron.Adv.Mater.10,2578(2008).[28]Y.Liao,X.Zhou,X.Xie,and Q.Yu,J.Mater.Sci.Mater.Electron.24,4427(2013).[29]B.A.Kang,K.S.Hwang,and J.H.Jeong,J.Sol-GelSci.Technol.43,145(2007).DOI:10.1063/1674-0068/29/cjcp1506116c⃝2016Chinese Physical Society。

对苯⼆甲酸锌Hydrothermal Synthesis and Crystal Structure of a Novel 2-Fold Interpenetrated Framework Based on Tetranuclear Homometallic ClusterRong-Yi Huang ?Xue-Jun Kong ?Guang-Xiang LiuReceived:15December 2007/Accepted:11January 2008/Published online:5March 2008óSpringer Science+Business Media,LLC 2008Abstract A novel 2-fold parallel interpenetrated polymer,Zn 2(OH)(pheno)(p -BDC)1.5áH 2O (1)(pheno =phenan-threne-9,10-dione;p -BDC =1,4-benzenedicarboxylate)was prepared by hydrothermal synthesis and characterized by IRspectra,elemental analysis and single crystal X-ray /doc/c97a12ccf61fb7360b4c65f3.html plex1crystallizes in the orthorhombic space group Pbca and affords a three-dimensional (3D)six-connected a -Ponetwork.Keywords Carboxylate ligand áHomometallic complex áa -Po1IntroductionIn the last decade,the construction by design of metal-organic frameworks (MOFs)using various secondary building units (SBUs)connected through coordination bonds,supramolecular contacts (e.g.,hydrogen bonding,p áááp stacking,etc.),or their combination has been an increasingly active research area [1].The design and controlled assembly of coordination polymers based on nano-sized MO(OH)clusters and multi-functional car-boxylates have been extensively developed for their crystallographic and potential applications in catalysis,nonlinear optics,ion exchange,gas storage,magnetism and molecular recognition [2].In most cases,multinu-clear metal cluster SBUs can direct the formation of novel geometry and topology of molecular architectureand help to retain the rigidity of the networks [3].A number of carboxylate-bridged metal clusters have been utilized to build extended coordination frameworks.Among these compounds,frameworks from multinuclear zinc cluster SBUs,including dinuclear (Zn 2)[4],trinu-clear (Zn 3)[5],tetranuclear (Zn 4)[6],pentanuclear (Zn 5)[7],hexanuclear (Zn 6)[8],heptanuclear (Zn 7) [9],and octanuclear (Zn 8)[10]clusters have attracted great interest and have been investigated extensively.Addi-tionally,a series of systematic studies on this subject has demonstrated that an interpenetrated array cannot prevent porosity,but enhances the porous functionalities of the supramolecular frameworks [11].More importantly,the research upsurge in interpenetration structures was pro-moted by the fact that interpenetrated nets have been considered as potential super-hard materials [12]and possess peculiar optical and electrical properties [13].Herein we present the synthesis,structure,and spectral properties of a new coordination polymer based on tetranuclear homometallic cluster,Zn 2(OH)(pheno)(p -BDC)1.5áH 2O (1).2Experimental2.1Materials and MeasurementsAll commercially available chemicals are reagent grade and used as received without further puri?cation.Sol-vents were puri?ed by standard methods prior to use.Elemental analysis for C,H and N were carried with a Perkin-Elmer 240C Elemental Analyzer at the Analysis Center of Nanjing University.Infrared spectra were obtained with a Bruker FS66V FT IR Spectrophotometer as a KBr pellet.R.-Y.Huang áX.-J.Kong áG.-X.Liu (&)Anhui Key Laboratory of Functional Coordination Compounds,College of Chemistry and Chemical Engineering,Anqing Normal University,Anqing 246003,P.R.China e-mail:liugx@/doc/c97a12ccf61fb7360b4c65f3.htmlJ Inorg Organomet Polym (2008)18:304–308DOI 10.1007/s10904-008-9199-72.2Preparation of Zn2(OH)(pheno)(p-BDC)1.5áH2O(1)A mixture containing Zn(NO3)2á6H2O(0.20mmol), p-1,4-benzenedicarboxylic acid(H2BDC)(0.20mmol), phenanthrene-9,10-dione(pheno)(0.10mmol)and NaOH (0.20mmol)in water(10mL)was sealed in a18mL Te?on lined stainless steel container and heated at150°C for72h.The reaction product was dark yellow block crystals of1,which were washed by deionized water sev-eral times and collected by?ltration;Yield,78%. Elemental Analysis:Calcd.for C24H15N2O10Zn2:C,46.33;H,2.43;N,4.50%.Found:C,46.38;H,2.47;N,4.48%.IR (KBr pellet),cm-1(intensity):3437(br),3062(m),1587(s),1523(m),1491(w),1424(m),1391(s),1226(w),1147 (w),1103(w),1051(w),875(w),843(m),740(w),728 (m),657(w).2.3X-ray Structure DeterminationThe crystallographic data collections for complex1were carried out on a Bruker Smart Apex II CCD with graphite-monochromated Mo-K a radiation(k=0.71073A?)at 293(2)K using the x-scan technique.The data were inte-grated by using the SAINT program[14],which also did the intensities corrected for Lorentz and polarization effects.An empirical absorption correction was applied using the SADABS program[15].The structures were solved by direct methods using the SHELXS-97program; and,all non-hydrogen atoms were re?ned anisotropically on F2by the full-matrix least-squares technique using the SHELXL-97crystallographic software package[16,17]. The hydrogen atoms were generated geometrically.All calculations were performed on a personal computer with the SHELXL-97crystallographic software package[17].The details of the crystal parameters,data collection and re?nement for four compounds are summarized in Table1. Selected bond lengths and bong angles for complex1are listed in Table2.3Results and DiscussionThe X-ray diffraction study for1reveals that the material crystallizes in the orthorhombic space group Pbca and features a2-fold parallel interpenetrated3D?3D net-work motif.The asymmetric unit contains two Zn(II) atoms,one hydroxyl,one pheno ligand,one and half of p-BDC molecules and one solvent water molecule.Selected bond lengths for1are listed in Table2.As shown in Fig.1, the Zn1ion,which is in the center of a tetrahedral geom-etry,is surrounded by three carboxylic oxygen atoms (Zn–O=1.918(5)–1.964(5)A?)from three p-BDC ligands and one l3-OH oxygen atom(O9).The Zn–O distance is1.965(5)A?.Two nitrogen atoms(N1and N2)that belong to pheno,one p-BDC oxygen atom(O3A)and one hydroxyl oxygen atom(O9A)are ligated to the Zn2center in the equatorial plane with another oxygen atom(O9)that arises from the second hydroxyl group and one oxygen atom(O5)that arises from the second p-BDC molecule situated in the axial position.EachZn2lies approximately in the equatorial position with a maximum deviation (0.048A?)from the basal plane.In the structure,Zn–O and Zn–N bond distances are in the range of 2.0530(5)–2.112(5)and2.157(5)–2.184(2)A?,respectively. There exist two types of p-BDC found in1(Scheme1); namely,monobidentate bridging(l3)and bi-bidentatebridging(l4)coordination modes.The bidentate bridging p-BDC connects mixed metals,where the smallest ZnáááZn distance is3.163A?,to complete a homodinuclear cluster, which is further linked by l3-OH into a six-connected Table1Crystal data and summary of X-ray data collection for1Zn2(pheno)(OH)(BDC)1.5áH2O Empirical formula C24H15N2O10Zn2Molecular mass/g mol-1622.12Color of crystal Dark yellowCrystal fdimensions/mm0.1890.1690.12 Temperature/K293Lattice dimensionsa/A?18.777(9)b/A?13.657(6)c/A?19.983(9)a/°90b/°90c/°90Unit cell volume(A?3)5125(4)Crystal system OrthorhombicSpace group PbcaZ8l(Mo-K a)/mm-1 1.931D(cacl.)/g cm-3 1.613Radiation type Mo-K aF(000)2504Limits of data collection/° 2.04B h B25.05Total re?ections24155Unique re?ections,parameters4545,347No.with I[2r(I)2821R1indices[I[2r(I)]0.0657w R2indices0.1858Goodness of?t 1.060Min/max peak(Final diff.map)/e A?-3-0.658/2.322tetranuclear cluster that is jointly coordinated by six p-BDC molecules(Fig.2).The clusters are further extended by p-BDC into a single3D framework(Fig.3).For clarity, we used the topological method to analyze this3D framework.Thus,the six-connected SBU is viewed to be a six-connected node.Furthermore,based on consideration of the geometry of thisnode,the3D frame is classi?ed as an a-Po net with41263topology(Fig.4).Of particular interest,the most intriguing feature of complex1is that a pair of identical3D single nets is interlocked with each other,thus directly leading to the formation of a2-fold interpenetrated3D?3D architecture(Fig.4)and the two pcu(a-Po)frameworks are related by a screw axis21[18]. Recently,a complete analysis of3D coordination networks shows that more than50interpenetrated pcu(a-Po)frames have been documented in the CSD database[18],including 2-fold,3-fold[19],and4-fold[20]interpenetration.In addition,several non-interpenetration motifs with a-Po topology have been reported to date[21].ZnZnO ZnZnZnZnO Znbidentate bidentate bidentate monodentateI IIScheme1Coordination modesof the bdc ligands in the structure of1;I is bis(bidentate),II is bi/monodentateFig.1ORTEP representation of complex1(the H atoms have been omitted for the sake of clarity).The thermal ellipsoids are drawn at 30%probabilityTable2Selected bond lengths(A?)and angles(°)for1Symmetry transformations usedto generate equivalent atoms:#1x-1/2,y,-z+1/2;#2-x,-y+1,-z;#3-x+1/2,-y+1,z-1/2Zn(1)–O(1) 1.918(5)Zn(2)–O(9)#2 2.091(4)Zn(1)–O(4)#1 1.953(5)Zn(2)–O(9) 2.103(5)Zn(1)–O(6) 1.964(5)Zn(2)–O(3)#3 2.112(5)Zn(1)–O(9) 1.965(5)Zn(2)–N(1) 2.157(6)Zn(2)–O(5)#2 2.053(5)Zn(2)–N(2) 2.184(6)O(1)–Zn(1)–O(4)#197.9(2)O(9)–Zn(2)–O(3)#388.81(18)O(1)–Zn(1)–O(6)112.9(2)O(5)#2–Zn(2)–N(1)94.7(2)O(4)#1–Zn(1)–O(6)104.7(2)O(9)#2–Zn(2)–N(1)170.7(2)O(1)–Zn(1)–O(9)122.9(2)O(9)–Zn(2)–N(1)91.6(2)O(4)#1–Zn(1)–O(9)109.7(2)O(3)#3–Zn(2)–N(1)88.9(2)O(6)–Zn(1)–O(9)107.0(2)O(5)#2–Zn(2)–N(2)87.1(2)O(5)#2–Zn(2)–O(9)#291.9(2)O(9)#2–Zn(2)–N(2)98.3(2)O(5)#2–Zn(2)–O(9)173.72(19)O(9)–Zn(2)–N(2)94.5(2)O(9)#2–Zn(2)–O(9)81.82(19)O(3)#3–Zn(2)–N(2)164.3(2)O(5)#2–Zn(2)–O(3)#391.3(2)N(1)–Zn(2)–N(2)75.7(2)O(9)#2–Zn(2)–O(3)#397.42(19)Fig.2Polyhedral representation of the homotetranuclear unit as asix-connected node linked by p-BDC ligandsMoreover,rich inter and intra hydrogen-bonds between the water molecules and the carboxylate groups (Table 3)further strengthen the stacking of the supra-architecture (Fig.5).4Supplementary MaterialsCrystallographic data (excluding structure factors)for thestructures reported in this paper have been deposited with the Cambridge Crystallographic Data Center as supple-mentary publication /doc/c97a12ccf61fb7360b4c65f3.html DC-666555.Copies of the data can be obtained free of charge on application to CCDC,12Union Road,Cambridge CB21EZ,UK (Fax:+44-1223-336033;e-mail:deposit@/doc/c97a12ccf61fb7360b4c65f3.html ).Acknowledgments This work was supported by the National Nat-ural Science Foundation of China (20731004)and the Natural Science Foundation of the Education Committee of Anhui Province,China(KJ2008B004).Fig.3Polyhedral presentation of one set of the 3D network along a -axis (a )and b -axis (b )Table 3Distance (A ?)and angles (°)of hydrogen bonding for com-plex 1D–H áááADistance of D áááA (A ?)Angle of D–H–A (°)O1W–H1WB áááO2#1 2.677(9)164O9–H19áááO1W#2 2.841(9)151C13–H13áááO3#3 3.045(10)121C22–H22áááO1W#43.353(10)167Symmetry transformations used to generate equivalent atoms:#1x,y,1+z;#2-x,1-y,-1+z;#3-x+1/2,-y+1,z -1/2;#4-x,1-y,1-zFig.4Simpli?ed schematic representation of the 3D ?3D two-fold interpenetrated a -Po network in1Fig.5Projection of the structure of 1along b -axis (dotted lines represent hydrogen-bonding)References1.(a)P.J.Hagrman,D.Hagrman,J.Zubieta,Angew.Chem.Int.Ed.38,2638(1998);(b)S.Leininger,B.Olenyuk,P.J.Stang,Chem.Rev.100,853(2000);(c)A.Erxleben,Coord.Chem.Rev.246, 203(2003);(d)K.Biradha,Y.Hongo,M.Fujita,Angew.Chem. Int.Ed.39,3843(2000);(e)P.D.Harey,H.B.Gray,J.Am.Chem.Soc.110,2145(1988);(f)D.Cave,J.M.Gascon,A.D.Bond,S.J.Teat,P.T.Wood,/doc/c97a12ccf61fb7360b4c65f3.html mun.1050(2002);(g)F.A.AlmeidaPaz,J.Klinowski,Inorg.Chem.43,3882(2004);(h)K.Biradha, Y.Hongo,M.Fujita,Angew.Chem.Int.Ed.39,3843(2000);(i) M.Eddaoudi,J.Kim,N.Rosi,D.Vodak,J.Wachter,M.O’Ke-egge,O.M.Yaghi,Science295,469(2002);(j)S.Q.Zhang,R.J. Tao,Q.L.Wang,N.H.Hu,Y.X.Cheng,H.L.Niu,W.Lin,J.Am.Chem.Soc.123,10395(2001);(k)L.Carlucci,G.Ciani,D.M.Proserpio,Cryst.Growth Design5,37(2005)2.(a)M.Eddaoudi,D.B.Moler,H.Li,B.Chen,T.M.Reineke,M.O’Keeffe,O.M.Yaghi,Acc.Chem.Res.34,319(2001);(b)P.J.Hagrman,D.Hagrman,J.Zubieta,Angew.Chem.Int.Ed.38, 2638(1999);(c)O.R.Evans,W.Lin,Acc.Chem.Res.35,511 (2002);(d)S.Kitagawa,R.Kitaura,S.Noro,Angew.Chem.Int.Ed.43,2334(2004);(e)S.L.James,Chem.Soc.Rev.32,276 (2003);(f)L.Pan,H.Liu,X.Lei,X.Huang,D.H.Olson,N.J.Turro,J.Li,Angew.Chem.Int.Ed.42,542(2003)3.(a)G.Ferey,C.Mellot-Draznieks,C.Serre,/doc/c97a12ccf61fb7360b4c65f3.html lange,Acc. Chem.Res.38,217(2005);(b)M.Eddaoudi,J.Kim,J.B.Wachter,H.K.Chae,M.O’Keeffe,O.M.Yaghi,J.Am.Chem.Soc.123,4368(2001);(c)M.Eddaoudi,J.Kim,M.O’Keeffe, O.M.Yaghi,J.Am.Chem.Soc.124,376(2002);(d)A.Thiru-murugan,S.Natarajan,Cryst.Growth Design6,983(2006);(e) R.Murugavel,M.G.Walawalkar,M.Dan,H.W.Roesky,C.N.R. Rao,Acc.Chem.Res.37,763(2004)4.(a)J.Kim,B.Chen,T.M.Reineke,H.Li,M.Eddaoudi,D.B.Moler,M.O’Keeffe,O.M.Yaghi,J.Am.Chem.Soc.123,8239 (2001);(b)J.J.Lu,A.Mondal,B.Moulton,M.Zaworotko,An-gew.Chem.Int.Ed.40,2113(2001)5.(a)Q.R.Fang,X.Shi,G.Wu,G.Tain,G.S.Zhu,R.W.Wang,S.L.Qiu,J.Solid State Chem.176,1(2003);(b)H.Li,C.E.Davis,T.L.Groy,D.G.Kelley,O.M.Yaghi,J.Am.Chem.Soc.120,2186(1998)6.(a)M.Eddaoudi,J.Kim,N.Rosi,D.Vodak,J.Wachter,M.O’Keeffe,O.M.Yaghi,Science295,469(2002);(b)B.Kesanli,Y.Cui,M.R.Smith,E.W.Bittner,B.C.Bockrath,W.B.Lin, Angew.Chem.Int.Ed.44,72(2005)7.Q.R.Fang,G.S.Zhu,Z.Jin,M.Xue,X.Wei,D.J.Wang,S.L.Qiu,Cryst.Growth Design7,1035(2007)8.C.Lei,J.G.Mao,Y.Q.Sun,H.Y.Zeng,A.Clear?eld,Inorg.Chem.42,6157(2003)9.J.R.Li,Y.Tao,Q.Yu,X.H.Bu,/doc/c97a12ccf61fb7360b4c65f3.html mun.1527(2007)10.S.Y.Yang,L.S.Long,R.B.Huang,L.S.Zheng,/doc/c97a12ccf61fb7360b4c65f3.html mun.472(2002)11.T.M.Reineke,M.Eddaoudi,D.M.Moler,M.O’Keeffe O.M.Yaghi,J.Am.Chem.Soc.122,4843(2002)12.D.M.Proserpio,R.Hoffman,P.Preuss,J.Am.Chem.Soc.116,9634(1994)13.(a)O.Ermer,Adv.Mater.3,608(1991);(b)/doc/c97a12ccf61fb7360b4c65f3.html ler,Adv.Mater.13,525(2001)14.SAINT version6.02a,Software Reference Manual(Bruker AXSInc.,Madison,W1,2002)15.G.M.Sheldrick,SADABS:Program for Empirical AbsorptionCorrection of Area Detector Data(University of Go¨ttingen, 1996)16.G.M.Sheldrick,SHELXS-97:Program for Crystal StructureSolution(University of Go¨ttingen,1997)17.G.M.Sheldrick,SHELXL-97:Program for Crystal StructureRe?nement(University of Go¨ttingen,1997)18.V.A.Blatov,L.Carlucci,G.Ciani,D.M.Proserpio,Cryst.Eng.Comm.6,377(2004)19.(a)B.F.Hoskins,R.Robson,N.V.Y.Scarlett,J.Chem.Soc./doc/c97a12ccf61fb7360b4c65f3.html mun.2025(1994);(b)E.Siebel,R.D.Fischer,Chem. Eur.J.3,1987(1997);(c)B.F.Abrahams,B.F.Hoskins,R.Robson,D.A.Slizys,/doc/c97a12ccf61fb7360b4c65f3.html m.4,478(1997);(d)M.J. Plater,M.R.S.J.Foreman,J.M.S.Skakle,Cryst.Eng.4,293 (2001);(e)X.L.Wang,C.Qin,E.B.Wang,Z.M.Su,Chem.Eur. J.12,2680(2006)20.B.Kesanli,Y.Cui,R.Smith,E.Bittner,B.C.Bockrath,W.Lin,Angew.Chem.Int.Ed.117,74(2005)21.(a)H.L.Gao,L.Yi,B.Ding,H.S.Wang,P.Cheng,D.Z.Liao,S.P.Yan,Inorg.Chem.45,481(2006);(b)Y.H.Wen,J.Zhang, X.Q.Wang,Y.L.Feng,J.K.Cheng,Z.J.Li,Y.G.Yao,New J. Chem.29,995(2005);(c)H.L.Sun,B.Q.Ma,S.Gao,S.R.Batten,Cryst.Growth Design5,1331(2005);(d)J.Yang,J.F.Ma,Y.Y.Liu,S.L.Li,G.L.Zheng,Eur.J.Inorg.Chem.2174 (2005)。

广西师范大学硕士学位论文水热法合成无机半导体纳米材料及其掺杂稀土发光纳米材料姓名：陶萍芳申请学位级别：硕士专业：无机化学指导教师：方岳平20080501陶萍芳广西师范大学硕士学位论文 2008水热法合成无机半导体纳米材料及其稀土发光纳米材料2005级无机化学纳米材料方向研究生：陶萍芳导师：方岳平中文摘要水热溶剂热制备技术是一种设备简单、操作容易的常用制备手段。

该法的主要优势在于多数材料能够在临近临界点的加热加压系统下，在一种适宜的溶剂中溶解。

自Heath及其合作者开拓了利用溶剂热法制备半导体纳米线的新方法之后，这种方法就被广泛的用于一维和空心纳米结构材料的合成与研究工作。

因此，我们选择水热法作为我们的制备手段。

本论文研究的主要目在于通过简单的水热法，探索合成不同的无机半导体纳米材料和稀土发光材料，通过对反应产物的各种测试表征结果进行分析，结合一些常见的生长机制，提出合理的模型来解释合成的纳米材料的生长机制；同时，对合成的纳米材料进行了性能测试，以期待制备的材料具有特别的物理性质。

论文的主要内容介绍如下：第一章简单介绍了纳米材料及其发展过程，叙述了纳米材料的性质、制备方法、表征手段以及稀土发光材料的研究进展。

对纳米材料的合成现状进行了概述，重点介绍了水热法在纳米材料的合成中的应用。

第二章简单介绍了通过无模板和表面活性剂技术，用水热法成功的制备了碲化银纳米管。

制备的样品用X-射线粉末衍射（XRD），场发射扫描电镜（SEM），透射电子显微镜（TEM），X-射线光电子能谱（XPS）和拉曼光谱表征。

探讨了碲化银晶型转变。

并基于低温β-碲化银内在的晶体结构提出了卷曲机理来解释碲化银纳米管的形成过程。

拉曼光谱分析表明，样品显示出有趣的拉曼散射增强现象。

第三章主要是采用简单的溶液-液相-固相（SLS）方法，一步合成了围绕金属Sn核垂直生长出一层In(OH)3纳米棒的蒲公英状核壳微球（Sn@[In(OH)3纳米棒]）。

铝掺杂对ZnO纳米线结构和光学性质的影响魏平;高红;姜威;卢会清;张春志【摘要】利用化学气相沉积方法成功地合成了不同Al掺杂浓度的ZnO纳米线.从场发射扫描电子显微镜可以看出纳米线的直径约为100nm.X射线衍射结果表明主要的衍射峰都与ZnO的晶面对应,为纤锌矿结构.当掺杂浓度达到2.0 at%时,在背散射拉曼光谱中观察到由于Al掺杂而引起的640 cm-1处的峰.光致发光谱表明,随着掺杂浓度的增加,紫外与可见发光的强度比值逐渐变小.【期刊名称】《哈尔滨师范大学自然科学学报》【年(卷),期】2010(026)003【总页数】3页(P53-55)【关键词】ZnO;Al纳米线;掺杂;光致发光;拉曼光谱【作者】魏平;高红;姜威;卢会清;张春志【作者单位】哈尔滨师范大学;哈尔滨师范大学;哈尔滨师范大学;大庆石油学院华瑞学院;大庆石油学院华瑞学院【正文语种】中文一维 ZnO纳米材料在功能材料领域得到了广泛的研究,并取得了一定的成果,被认为是一种很有应用前景的材料.因为 ZnO具有较高的激子束缚能 (60meV)和较大的带隙宽度(3.37 eV)[1],在发光二极管和紫外激光器[2-6]等器件中有广泛的应用.此外,通过在 ZnO中掺入 Ga,In,Sn,Al等元素,能有效改善半导体的电学、光学和磁学性能,可广泛应用于紫外光发射、变阻器、压电转换器、传感器、透明高功率电子设备和声表面波器件等[7-9].研究表明,ZnO中掺入Al后,电导率增加,在透明电极等方面有重要的应用前景.目前,关于ZnO∶Al薄膜的研究报道很多[10-12],但是关于ZnO∶Al的一维纳米结构的报道较少,其中 S.N.Bai等人利用水热法合成了Al 掺杂的 ZnO纳米线[13],一维ZnO∶Al纳米材料的结构和性质研究,将为实现透明光电器件的纳米化奠定实验基础.以 ZnO粉和 Al粉为前驱物,采用化学气相沉积(CVD)方法合成了不同 Al掺杂浓度的 ZnO纳米线,并对其结构、光学性质等进行了研究.Al掺杂 ZnO纳米线的合成是用 CVD方法在高温管式炉中完成的.以 ZnO粉和 Al 粉作为前驱物,置于高温管式炉最高温度处,镀金的Si片作为衬底置于管式炉的下游.抽真空后,加热,以8℃/min的速度升温至1400℃,恒温 5 min,然后整个系统自然冷却至室温.在此过程中始终保持高温炉内压强为 200 Pa,载气 (Ar)流量为100sccm(standard cubic centimeter per minute).最后在下游的衬底上得到一层白色的产物.利用场发射扫描电子显微镜 (FE-SEM,S-4800,Hitachi),X射线衍射仪(XRD,D∕ MAX 2200,Japan)对合成的 ZnO纳米结构的形貌和晶体结构进行表征.并用拉曼光谱仪 (J-Y,France)采用背散射方式以波长为488 nm的 Ar+激光器为激发光源,对样品进行拉曼光谱测量.以波长为325 nm的 He-Cd激光器为激发光源,测量样品的室温光致发光(Photoluminescence,简称 PL).样品的形貌由场发射扫描电子显微镜表征.图 1(a)为合成的样品的 SEM图,可以看出纳米线产量高,尺寸均匀,直径约为 100～200 nm,长度可达几十微米.随 Al浓度增加,样品的形貌无明显变化 (图略).图 1(b)为 Al掺杂 ZnO的 X射线能谱图(EDS),结果表明纳米线中有 Al,Zn, O元素.为了研究Al浓度对 ZnO纳米线结构性质的影响,图 2给出 Al掺杂浓度分别为 0.7 at%、2.0 at%、5.0 at%、10 at%的 X射线衍射谱,可以看出,当掺杂浓度为 0.7 at%时,所有衍射峰都与ZnO的晶面对应,为纤锌矿结构.当达到 2.0 at%时,主要的衍射峰仍与 ZnO的晶面对应,同时有非常弱的 ZnAl2O4相出现,表明在实验过程中有少量 ZnAl2O4被合成.此外,在四个谱图中,与ZnO对应的主要衍射峰都向大角度方向移动,表明由于铝掺杂使得沿 c轴晶格常数变小.这种情况经常存在于掺杂的晶体中,把这种现象归因于杂质原子周围局部应力增加或与杂质原子有关的点缺陷的增加[14].图 3给出上述四个样品的拉曼谱,在437cm-1处的最强峰是 ZnO的 E2(high)模式,这个模式越强,表明晶体质量越好.而且,与纯 ZnO对比,我们发现当掺杂浓度达到2.0 at%时,在约为 640 cm-1处出现一个峰,这个峰是由于Al掺杂而引起的[15].当掺杂浓度增大到 10 at%时,发现640 cm-1处的峰位范围变大,在约为 660 cm-1处出现一个峰,同时,ZnO的 E2(high)模式非对称展宽,在 420 cm-1处出现一个新峰,这两个峰与Al掺杂过量有关,这与 XRD结果相符合.为了研究不同Al掺杂浓度对 ZnO纳米结构光学性质的影响,对四个样品进行室温光致发光测试.从图4中可以看出,当掺杂浓度小于 2.0 at%时,只有一个强的紫外发射峰,来源于 ZnO自由激子辐射复合.当掺杂浓度达到 2.0 at%时,有微弱的可见发光峰出现.而当掺杂浓度达到5.0 at%时,明显有两个发光峰,近紫外发射峰和宽的可见发光峰.可能是由于掺杂Al而增加了氧空位的浓度,使得可见光增强.光致发光谱表明,不同Al掺杂浓度对ZnO纳米线的发光有一定的影响,当掺杂浓度超过2.0 at%时,紫外峰相对强度明显降低.利用 CVD方法合成了不同 Al掺杂浓度的ZnO纳米线,纳米线的直径约为 100 nm,X射线衍射谱表明主要的衍射峰都与 ZnO的晶面对应,背散射拉曼光谱反应出样品的晶体质量较高,同时观察到Al掺杂引起的 640 cm-1处的峰.从室温光致发光谱中可观察到随着掺杂浓度的增加,紫外与可见发光的强度比值逐渐变小,可能是由于掺杂Al而增加了氧空位的浓度,使得可见光增强.Al-doped ZnO nanowiresof different concentrationwere successfully synthesized on silicon substrates via chemical vapor deposition.The nanowires had uniform size of 100 nm.X-ray diffraction analysis demonstrated that the majorpeaks attributed to the wurtzite ZnO.Raman scattering showed thatAl doping induces vibration mode of 640 cm-1(Al≥2.0 at%).The photoluminescence spectra indicate that the intensity ratio of the UV to green emission was decreased as the Al concentration increases.【相关文献】[1] Yang L.,Wang G.,Tang C.,Wang H.,Zhang L.Chem. Phys.Letts.2005,409:337.[2] Tsukazaki A.,Ohtomo A.,Onuma T.,et al.Nat.Mater. 2005,4:42.[3] Look D.C..Mater.Sci.Eng.B,2001,80:383.[4] D.C.Look,B.Claflin.Phys.Status Solidi B,2004,241: 624.[5] Pearton S.J.,NortonD.P.,Ip K.,et al.Prog.Mater.Sci, 2005,50:293.[6] Pearton S.J.,Heo Y.W.,IvillM.,et al.Semicond.Sci. Technol,2004,19:R59.[7] Jie J.S,Wang G.Z,Han X.H.Chem.Phys.Lett.2004, 387,466.[8] Bae S.Y,Na C.W,Kang,J.H,Park J.J.Phys.Chem.B 2005,109,2526.[9] Liu J,Zhang Y,Qi J,Huang Y,Zhang X,Liao,Q.Mater. Lett.2006,60,2623.[10]Bamiduro O.,Mustafa H.,Mundle R.,Konda R.B.,and PradhanA.K.Appl.Phys.Lett.,2007,90:252108.[11]Singh A.V.,KumarManoj.,Mehra R.M.,Wakahara Akihiro,and Yoshida Akira.J.India Inst.Sci,2001,81:527.[12]Pei Z.L.,Sun C.,TanM.H.,Xiao J.Q.,Guan D.H., Huang R.F.,andWen L.S.Journal of Appl.Phys,2001, 90:3432.[13]Bai S.N.,TsaiH.H.,Tseng T.Y.Thin Solid Films,2007, 516:155-158.[14]Ohkawa K.,Mitsuyu T.,YamazakiO.J.Appl.Phys,1987, 62:3216.[15]Lo Shihshou,Huang Dison,Tu Chun Hsiang,Hou Chiahung, ChenChiichang.J.Phys.D:Appl.Phys,2009,42:095420.。

Scientists studying the effects of various phenomena play a crucial role in expanding our understanding of the natural world, human behavior, and the complex interplay between different variables. This process involves systematic investigation, data collection, analysis, and interpretation to draw meaningful conclusions. Let's explore the broader concept of scientists studying the effects of different factors and delve into the methodologies, significance, and challenges associated with such studies.### **Introduction:**Scientists engaging in the study of effects often aim to uncover causal relationships, identify patterns, or understand the impact of certain factors on a given system. This exploration encompasses a wide range of disciplines, including physics, chemistry, biology, psychology, environmental science, and social sciences. The effects being studied can be diverse, ranging from the microscopic level of particles to the macroscopic level of ecosystems or human societies.### **Methodologies in Studying Effects:**1. **Experimental Design:**- **Controlled Experiments:** Scientists often use controlled experiments to isolate specific variables and observe their effects systematically. This involves manipulating one variable while keeping others constant.2. **Observational Studies:**-**Longitudinal Studies:** Researchers track subjects over an extended period to observe changes and identify potential causative factors.- **Cross-Sectional Studies:** Examining a diverse group at a single point in time to uncover correlations and associations.3. **Field Studies:**-**Ecological Studies:** Scientists study effects within natural environments, observing interactions between organisms and their surroundings.-**Social Science Field Studies:** Researchers may conduct surveys or interviews to understand the effects of social, economic, or cultural factors on individuals or communities.4. **Computer Modeling:**- **Simulation Studies:** Scientists use computer models to simulate real-world scenarios, allowing them to predict and analyze potential effects without real-world experimentation.### **Significance of Studying Effects:**1. **Scientific Advancement:**- **New Discoveries:** Research on the effects of various factors often leads to the discovery of new phenomena, principles, or relationships.-**Advancement of Knowledge:** Building on existing knowledge, scientists contribute to the continuous advancement of their respective fields.2. **Problem Solving:**- **Environmental Solutions:** Studying the effects of human activities on the environment aids in developing strategies for sustainable resource use and conservation.- **Medical Breakthroughs:** Understanding the effects of drugs, diseases, and lifestyle on health contributes to medical advancements and improved healthcare.3. **Policy Formulation:**-**Informed Decision-Making:** Governments and organizations use scientific studies to formulate policies addressing societal issues, such as public health, education, and environmental protection.-**Risk Assessment:** Studying the effects of potential hazards helps in assessing and mitigating risks to human health and safety.4. **Technological Innovation:**- **Materials Science:** Studying the effects of different materials on each other contributes to the development of new materials with enhanced properties.-**Engineering Advancements:** Understanding the effects of forces, temperature, and other factors on structures and systems informs engineering practices and innovations.### **Challenges in Studying Effects:**1. **Complexity of Systems:**-**Interconnected Variables:** Natural systems are often complex, with numerous interconnected variables. Isolating the effect of one variable while keeping others constant can be challenging.2. **Ethical Considerations:**- **Human Subjects:** In social and medical studies, ethical considerations, such as informed consent and the potential for harm, must be carefully addressed.-**Environmental Impact:** Researchers studying ecological effects must consider the potential impact of their studies on the environment.3. **Resource Limitations:**-**Financial Constraints:** Conducting comprehensive studies requires financial resources for equipment, personnel, and data analysis.- **Time Constraints:** Longitudinal studies, in particular, can be time-consuming, requiring sustained funding and commitment.4. **Data Interpretation:**-**Statistical Challenges:** Interpreting data and drawing meaningful conclusions require statistical expertise to avoid misinterpretation or bias.- **Correlation vs. Causation:** Distinguishing between correlation and causation is critical to avoid drawing incorrect causal relationships.### **Case Study: Studying the Effects of Climate Change:**Consider a case study where scientists are studying the effects of climate change:1. **Methodology:**- **Observational Studies:** Scientists analyze long-term climate data, including temperature records, sea-level measurements, and ice core samples.-**Computer Modeling:** Climate scientists use sophisticated models to simulate future climate scenarios based on different emission scenarios.2. **Significance:**- **Policy Impact:** Findings contribute to global efforts to mitigate climate change, shaping international agreements and policy decisions.-**Environmental Awareness:** Studying the effects raises public awareness of climate change impacts, fostering environmentally conscious behaviors.3. **Challenges:**- **Data Uncertainty:** Climate systems are intricate, and uncertainties in data interpretation can pose challenges in predicting future scenarios.- **Global Collaboration:** Studying a phenomenon as pervasive as climate change requires international collaboration and coordination.### **Conclusion:**In conclusion, scientists studying the effects of various factors contribute significantly to human knowledge, technological innovation, and policy formulation across diverse disciplines. The methodologies employed, the significance of their findings, and the challenges they face vary depending on the field of study. Despite challenges, the pursuit of understanding the effects of different variables remains integral to scientific progress and addressing global challenges.。

将较稳定的金属氧化物作为电子传输层材料[6]㊂目前,大部分高效率乃至创纪录的PSCs 都是基于SnO 2(Tin Dioxide)传输层制备的㊂旋涂稀释的商业SnO 2水分散溶液后进行退火,可成功地形成致密均匀的SnO 2膜[7⁃9]㊂然而,这种SnO 2纳米晶体分散在水溶液并不稳定,由于范德华相互作用,SnO 2纳米颗粒容易发生团聚,制备得到的SnO 2薄膜的电学和表面性能也会受到影响[10]㊂对SnO 2传输层进行掺杂是一种有效改善薄膜性能的策略,掺杂材料是多样的,包括有机无机盐,有机小分子材料和有机聚合物等[11⁃13]㊂基于上述,笔者利用一种小分子螯合剂柠檬酸钠(SC:Sodium Citrate)对SnO 2传输层进行掺杂,以提高器件的性能㊂SC 是一种常见的螯合剂,3个羧酸基团可以与Sn 4+发生螯合作用,以稳定SnO 2水分散液,Na +可以提升SnO 2的导电性㊂SnO 2薄膜的粗糙度降低,浸润性增强,生长在SnO 2薄膜上的钙钛矿具有更大的晶粒尺寸和更好的结晶度㊂对器件进行一系列测试后发现,SC 的掺杂减少了器件中缺陷密度,抑制了载流子的复合,使电荷传输变得更加高效㊂PSCs 获得了21.53%的效率和良好的稳定性,与未掺杂SC 的器件相比有明显的提升㊂1　器件的制备流程与实验表征1.1　实验材料和器件结构该实验制备的PSCs 具有正型器件结构㊂阴极选用ITO(Indium Tin Oxide)导电玻璃,电子传输层为SnO 2㊂钙钛矿层的组成成分为FA 1-x MA x PbI 3,空穴传输层是经典的小分子材料Spiro⁃OMeTAD㊂阳极选用金属材料Au㊂在器件制备过程中将SC 掺杂到SnO 2中㊂最终的电池结构为ITO /SnO 2+SC /FA 1-x MA x PbI 3/Spiro⁃OMeTAD /Au㊂图1是本实验适用器件的结构和SC 的化学结构㊂图1　器件结构与SC 的化学结构Fig.1　Device structure and chemical structure of SC 1.2　器件制备流程1.2.1　ITO 基片处理首先将ITO 基片置于去离子水中超声处理10min,然后依次置于丙酮和异丙醇采用相同的方法处理,然后用氮气气流进行干燥,在制备SnO 2传输层前需要紫外臭氧处理30min㊂1.2.2SnO 2电子传输层制备SnO 2前驱液是将SnO 2纳米晶的水分散液和去离子水以1∶4体积比混合得到的,用移液枪吸取50μL 的SnO 2前驱液均匀地滴加在ITO 基底上,以3000r /min(Round Per Minute)的转速旋涂30s㊂在150℃下退火30min 以获得SnO 2电子传输层,自然冷却至室温㊂对掺杂了SC 的SnO 2电子传输层,将0.5㊁1和1.5mg 的SC 溶解在1mL 纯的SnO 2前驱体溶液中,然后以转速3000r /min 和时间30s 的参数进行旋涂,在150℃下退火30min 获得SC 掺杂的SnO 2电子传输层㊂1.2.3　钙钛矿层制备钙钛矿层通过两步法制备㊂首先,在1mL DMF (N,N⁃Dimethylformamide )和DMSO (Dimethyl Sulfoxide)(体积比V DMF ∶V DMSO =9∶1)的混合溶剂中将1.5mM 的PbI 2溶解,然后用移液枪吸取50μL 的PbI 2前驱体溶液均匀地滴加在SnO 2上㊂在2000r /min 的转速下旋涂30s,然后在70℃下退火1min㊂338第5期纪永成,等:基于柠檬酸钠掺杂SnO 2的钙钛矿太阳能电池438吉林大学学报(信息科学版)第41卷将100μL有机混合物的异丙醇溶液(FAI∶MAI∶MACl=90mg∶6.39mg∶9mg溶解在1mL异丙醇中)动态滴加在PbI2上,转速参数设置为2000r/min,时间参数设置为30s㊂之后将其转移到30%~40%RH(Relative Humidity)的条件下150℃退火15min,形成FA1-x MA x PbI3钙钛矿膜㊂1.2.4　Spiro⁃OMeTAD空穴传输层制备在400μL氯苯中溶解28.9mg Spiro⁃OMeTAD粉末直至澄清,然后加入7μL的LiTFSI(Bis (trifluoromethane)sulfonamide lithium salt)溶液(520mg/mL溶解于乙腈)和11.5μL的TBP(4⁃Tert⁃Butylpyridine),继续搅拌15h㊂在钙钛矿层上滴加30μL Spiro⁃OMeTAD溶液,转速参数设置为4000r/min,时间参数设置为30s,从而获得Spiro⁃OMeTAD空穴传输层㊂1.2.5　Au电极制备将样品放入真空沉积系统中,在真空度低于1.0×10-3Pa的条件下在空穴传输层之上沉积80nm厚的Au,完成器件制备㊂1.3　实验表征利用Shimadzu XRD⁃6000得到了钙钛矿膜的X射线衍射(XRD:X⁃Ray Diffraction)谱㊂在模拟太阳光和黑暗环境下,分别利用Keithley2601源表测量PSCs和电子器件的电流密度⁃电压(J⁃V:Current Density⁃Voltage)和电流⁃电压(I⁃V:Current⁃Voltage)曲线㊂利用ICON⁃PT仪器测量了SnO2膜的原子力显微镜(AFM:Atomic Force Microscope)图像㊂使用FTA200型动态接触角分析仪测量了PbI2前驱体溶液在SnO2薄膜上的接触角㊂通过JEOL JSM⁃7500场发射扫描电镜测得钙钛矿膜表面的扫描电子显微镜(SEM:Scanning Electron Microscopy)图像㊂通过荧光分光光度计和IHR320荧光瞬态光谱测试系统得到钙钛矿膜的光致发光(PL:Photoluminescence)光谱和时间分辨光致发光(TRPL:Time⁃Resolved Photo Luminescence)谱㊂使用Crowntech QTest Station1000ce测量了器件的入射光子⁃电子转换效率(IPCE: Incident Photon⁃electron Conversion Efficiency)光谱㊂利用UV⁃1700进行吸收光谱测试㊂2　实验结果与分析笔者利用AFM和电导率测试对SnO2薄膜的表面和电学性能进行了分析,如图2所示㊂首先,利用AFM对纯SnO2和SC掺杂的SnO2薄膜进行测量,以分析SC掺杂对薄膜表面形貌和粗糙度的影响㊂如图2a和图2b所示,ITO基底上的两种SnO2薄膜都是致密生长的,纯SnO2薄膜显示了2.29nm的均方根(RMS:Root⁃Mean⁃Square)粗糙度,SC的掺杂使薄膜的粗糙度下降到了2.10nm,这是由于SC和Sn4+的螯合作用稳定了SnO2纳米颗粒在水溶液中的均匀分散性,改善了薄膜形貌,这有利于和钙钛矿形成更好的接触[13⁃14]㊂然后测量了2种SnO2薄膜的导电性,图2c是2种电子器件的I⁃V曲线㊂根据公式I=σ0(A/d)V(σ0代表SnO2薄膜的电导率,A代表SnO2薄膜的有效面积,d代表SnO2薄膜的有效厚度)计算得到纯SnO2薄膜的电导率为3.00×10-3ms/cm,而引入SC后增长为3.75×10-3ms/cm[15],这是由于SC中的Na+对SnO2的掺杂提升了薄膜的电导率,使电荷的传输变得更加有效㊂图2　纯SnO2和SC掺杂的SnO2薄膜的AFM图像和电导率测试Fig.2　AFM images and conductivity test of pure SnO2and SC⁃doped SnO2films钙钛矿的生长结晶依赖于基底的表面特性,因此测量了PbI 2前驱体溶液在两种SnO 2薄膜上的接触角,如图3所示㊂PbI 2前驱体溶液在纯SnO 2薄膜上的接触角为38.81°,在引入SC 后,接触角减小到了28.53°㊂这说明SC 的掺杂改善了SnO 2薄膜的表面浸润性,有利于钙钛矿更好地生长结晶㊂图3　PbI 2前驱体溶液在SnO 2薄膜上的接触角Fig.3　Contact angle of PbI 2precursor solution on SnO 2films对生长在这2种SnO 2上的钙钛矿膜的特性进行了测量,如图4所示㊂图4a 和图4b 是钙钛矿膜的表面SEM 图像,生长在这2种SnO 2上的钙钛矿膜致密且均匀,没有明显的针孔㊂与生长在纯SnO 2上的钙钛矿相比,生长在SC 掺杂SnO 2上的钙钛矿具有更大的晶粒尺寸,有利于减少晶界缺陷㊂图4c 是钙钛矿膜的XRD 谱,2种钙钛矿膜都显示出α相钙钛矿的3个特征峰,分别是13.92°的(001)晶面峰㊁24.30°的(111)晶面峰㊁28.06°的(002)晶面峰以及12.62°的PbI 2峰[16⁃17]㊂可以发现,生长在SC 掺杂SnO 2上的钙钛矿膜具有更高的(001)晶面峰强度和更低的PbI 2/(001)峰强度比,这表明两步法制备过程中,PbI 2和有机卤化物更好地反应转化为钙钛矿㊂图4d 是钙钛矿膜的吸收光谱,在550~650nm 范围内,生长在SC 掺杂SnO 2上的钙钛矿膜具有更高的吸光度,这表明其可以更好地进行光吸收㊂上述测试结果表明,SC 的掺杂改善了SnO 2薄膜的特性,进而影响了钙钛矿膜的结晶过程,改善了钙钛矿膜的结晶质量㊂图4　钙钛矿膜的SEM 图像㊁XRD 谱和吸收光谱Fig.4　SEM images ,XRD spectra and absorption spectra of perovskite films 利用PL 和TRPL 可以更直接地分析样品中的电荷输运和复合情况,如图5所示㊂图5a 表明,2种钙钛矿膜的发射峰都出现在804nm 处㊂在SnO 2中掺杂SC 后,钙钛矿膜的PL 峰的强度发生了很强的538第5期纪永成,等:基于柠檬酸钠掺杂SnO 2的钙钛矿太阳能电池淬灭㊂钙钛矿膜是在SnO 2上制备的,PL 的淬灭说明SC 掺杂使电荷从钙钛矿向ITO 的输运速度加快㊂图5b 的TRPL 测试可以得出同样的结论,生长在SC 掺杂SnO 2上的钙钛矿膜表现出更快的PL 强度衰减,这是因为电荷传输加快,减少电荷积累,可以预料这将提升PSCs 的开路电压(V oc :Open⁃Circuit Voltage)和填充因子(FF:FillFactor)㊂图5　钙钛矿膜的PL 和TRPL 光谱Fig.5　PL and TRPL spectra of perovskite films 在对SnO 2和钙钛矿薄膜的特性进行测量后,笔者制备了相应的器件并测量了它们的光伏性能㊂图6a 和表1给出了基于不同浓度的SC 掺杂器件的J⁃V 特性曲线和关键参数㊂基于纯SnO 2制备的器件的V oc 为1.104V,短路电流密度(Short⁃Circuit Current Density,J sc )为24.02mA /cm 2,FF 为75.74%,功率转换效率(PCE:Power Conversion Efficiency)为20.08%㊂使用SC 对SnO 2进行掺杂后,器件的效率逐渐提升㊂当SC 的掺杂浓度为1.0mg /mL 时,器件获得了21.53%的最佳PCE,V oc 增长到了1.135V,J sc 略有提升,达到了24.25mA /cm 2,FF 增长为78.23%㊂器件在反向扫描和正向扫描下的迟滞现象如图6b 和表2所示㊂图6　器件的J⁃V 曲线㊁IPCE 光谱和PCE 分布Fig.6　J⁃V curves ,IPCE spectra and PCE distribution of devices 基于纯SnO 2的器件具有更明显迟滞㊂在反向扫描下的PCE 为20.08%,正向扫描下的PCE 为19.07%㊂而优化后的器件在反向扫描下的PCE 为21.53%,正向扫描下的PCE 为21.17%㊂迟滞因子(HI:Hysteresis Index)是对器件的迟滞效应进行量化的一个指标,公式为h HI =(p PCE 反向–p PCE 正向)/638吉林大学学报(信息科学版)第41卷p PCE 反向[18]㊂计算结果表明,掺杂SC 后,器件的HI 从5.03%下降到1.67%㊂器件效率的提升和迟滞的减小得益于器件中减少的缺陷和高效的电荷传输㊂图6c 给出了器件的IPCE 光谱㊂SC 掺杂SnO 2后,器件的IPCE 值在350~750nm 的波长范围内有明显提升,这与器件的J⁃V 曲线测试结果一致㊂2种器件由IPCE 曲线积分得到的电流分别为23.04和23.47mA /cm 2,低于J⁃V 曲线中的J sc ㊂这可能是由器件的迟滞和偏置效应导致[19⁃20]㊂图6d 是器件的PCE 分布㊂每种条件下选取10个独立的器件㊂与基于纯SnO 2的器件相比,基于SC 掺杂SnO 2的器件具有更高的PCE,且相应的分布最窄㊂这证实了使用这种策略法制备高性能PSCs的可靠性㊂表1　不同掺杂浓度下的器件的关键参数Tab.1　Key parameters of the devices with different doping concentrations浓度(mg㊃mL -1)V oc /V J sc /(mA㊃cm -2)FF /%PCE /%0 1.10424.0275.7420.080.5 1.12224.1577.0120.871.0 1.13524.2578.2321.531.5 1.12824.1077.8121.15表2　反向和正向扫描下器件的关键参数Tab.2　Key parameters of the devices under reverse and forward scanning 器件扫描方向V oc /V J sc /(mA㊃cm -2)FF /%PCE /%SnO 2反向 1.10424.0275.7420.08正向 1.08323.8473.8519.07SnO 2+SC 反向 1.13524.2578.2321.53正向 1.13424.1677.7821.17 笔者测量了器件的稳态PCE 输出和暗态J⁃V 曲线,结果如图7所示㊂图8为器件的稳定性测试结果㊂图7　器件的稳态PCE 输出和暗态J⁃V 曲线Fig.7　Stabilized PCEs and dark J⁃V curves of devices 图8　器件的稳定性测试Fig.8　Stability test of devices 从图7a 中可看出,基于纯SnO 2的器件的稳态PCE 输出为18.94%,经过SC 掺杂后,器件的稳态PCE 输出为21.02%㊂此外,基于SC 掺杂SnO 2的器件可以在更短的时间内达到稳定的输出,这是因为器件中的缺陷密度降低,电荷积累减少㊂图7b 是在黑暗环境中测量得到的器件的J⁃V 曲线,经SC 掺杂后,器件的暗电流密度显著降低,说明SC 掺杂有效地抑制了器件中的电流泄漏㊂这种有害的电流泄露主要是器件中有害杂质和缺陷引起的电荷复合导致的[21]㊂738第5期纪永成,等:基于柠檬酸钠掺杂SnO 2的钙钛矿太阳能电池838吉林大学学报(信息科学版)第41卷上述测试结果表明,SC掺杂减少了器件中的缺陷,因此器件的电荷传输得到改善,载流子复合引起的V oc和FF损失减少,PSCs的光伏性能得到了提高㊂最后,测量了器件的稳定性,结果如图8所示㊂将未封装的器件在黑暗和相对湿度为10%~20%的空气环境中放置240h后,基于纯SnO2的器件损失了20%的初始效率,而基于SC掺杂SnO2的器件可以保留93%的初始PCE,稳定性获得了显著的提升㊂3　结　语笔者利用SC对正型PSCs的SnO2传输层进行掺杂,提升了SnO2薄膜的电学和表面性能,进而获得了高质量的钙钛矿薄膜㊂在此基础上,制备了结构为ITO/SnO2+SC/FA1-x MA x PbI3/Spiro⁃OMeTAD/Au的PSCs㊂在最优的SC掺杂浓度1.0mg/mL下,器件的V oc,J sc和FF从1.104V,24.02mA/cm2和75.74%提升到了1.135V,24.25mA/cm2和78.23%,从而产生了21.53%的PCE㊂除了效率有明显提升以外,器件的稳定性也有显著增强㊂器件效率和稳定性的提升归因于器件中缺陷的减少和电荷传输的加速,这也通过相应的表征得到了证明㊂研究表明,利用SC掺杂SnO2是一种简单有效的提升PSCs性能的策略㊂参考文献:[1]GREEN M A,HO⁃BAILLIE A,SNAITH H J.The Emergence of Perovskite Solar Cells[J].Nature Photonics,2014,8(7): 506⁃514.[2]WEI H,FANG Y,MULLIGAN P,et al.Sensitive X⁃Ray Detectors Made of Methylammonium Lead Tribromide Perovskite Single Crystals[J].Nature Photonics,2016,10(5):333⁃339.[3]KIM Y C,KIM K H,SON D⁃Y,et al.Printable Organometallic Perovskite Enables Large⁃Area,Low⁃Dose X⁃Ray Imaging [J].Nature,2017,550(7674):87⁃91.[4]LIU Y,ZHANG Y,YANG Z,et al.Thinness⁃and Shape⁃Controlled Growth for Ultrathin Single⁃Crystalline Perovskite Wafers for Mass Production of Superior Photoelectronic Devices[J].Advanced Materials,2016,28(41):9204⁃9209. [5]GREEN M A,DUNLOP E D,SIEFER G,et al.Solar Cell Efficiency Tables(Version61)[J].Progress in Photovoltaics: Research and Applications,2023,31(1):3⁃16.[6]LIAN J,LU B,NIU F,et al.Electron⁃Transport Materials in Perovskite Solar Cells[J].Small Methods,2018,2 (10):1800082.[7]JIANG Q,ZHANG L,WANG H,et al.Enhanced Electron Extraction Using SnO2for High⁃Efficiency Planar⁃Structure HC (NH2)2PbI3⁃Based Perovskite Solar Cells[J].Nature Energy,2016,2(1):16177.[8]YOO J J,SEO G,CHUA M R,et al.Efficient Perovskite Solar Cells via Improved Carrier Management[J].Nature,2021, 590(7847):587⁃593.[9]MIN H,LEE D Y,KIM J,et al.Perovskite Solar Cells with Atomically Coherent Interlayers on SnO2Electrodes[J].Nature, 2021,598(7881):444⁃450.[10]YOU S,ZENG H,KU Z,et al.Multifunctional Polymer⁃Regulated SnO2Nanocrystals Enhance Interface Contact for Efficient and Stable Planar Perovskite Solar Cells[J].Advanced Materials,2020,32(43):2003990.[11]PARK M,KIM J⁃Y,SON H J,et al.Low⁃Temperature Solution⁃Processed Li⁃Doped SnO2as an Effective Electron Transporting Layer for High⁃Performance Flexible and Wearable Perovskite Solar Cells[J].Nano Energy,2016, 26:208⁃215.[12]WANG P,CHEN B,LI R,et al.Cobalt Chloride Hexahydrate Assisted in Reducing Energy Loss in Perovskite Solar Cells with Record Open⁃Circuit Voltage of1.20V[J].ACS Energy Letters,2021,6(6):2121⁃2128.[13]YANG D,YANG R,WANG K,et al.High Efficiency Planar⁃Type Perovskite Solar Cells with Negligible Hysteresis Using EDTA⁃Complexed SnO2[J].Nature Communications,2018,9(1):3239.[14]TAO J,LIU X,SHEN J,et al.Functionalized SnO2Films by Using EDTA⁃2M for High Efficiency Perovskite Solar Cells with Efficiency over23%[J].Chemical Engineering Journal,2022,430:132683.[15]LIU X,WU Z,ZHANG Y,et al.Low Temperature Zn⁃Doped TiO2as Electron Transport Layer for19%Efficient Planar Perovskite Solar Cells[J].Applied Surface Science,2019,471:28⁃35.[16]QIUF Z,LI M H,WANG S,et al.Regulating the Crystalline Phase of Intermediate Films Enables FA 1-x MA x PbI 3Perovskite Solar Cells with Efficiency over 22%[J].Journal of Materials Chemistry A,2021,9(42):24064⁃24070.[17]MA F,LI J,LI W,et al.Stable α/δPhase Junction of Formamidinium Lead Iodide Perovskites for Enhanced Near⁃InfraredEmission [J].Chemical Science,2017,8(1):800⁃805.[18]XIONG Q,WANG C,ZHOU Q,et al.Rear Interface Engineering to Suppress Migration of Iodide Ions for Efficient PerovskiteSolar Cells with Minimized Hysteresis [J].Advanced Functional Materials,2022,32(7):2107823.[19]WU M C,CHAN S H,JAO M H,et al.Enhanced Short⁃Circuit Current Density of Perovskite Solar Cells Using Zn⁃DopedTiO 2as Electron Transport Layer [J].Solar Energy Materials and Solar Cells,2016,157:447⁃453.[20]WANG F,YU H,XU H,et al.HPbI 3:A New Precursor Compound for Highly Efficient Solution⁃Processed Perovskite SolarCells [J].Advanced Functional Materials,2015,25(7):1120⁃1126.[21]WETZELAAER G⁃J A H,SCHEEPERS M,SEMPERÉA M,et al.Trap⁃Assisted Non⁃Radiative Recombination in Organic⁃Inorganic Perovskite Solar Cells [J].Advanced Materials,2015,27(11):1837⁃1841.(责任编辑:刘俏亮)938第5期纪永成,等:基于柠檬酸钠掺杂SnO 2的钙钛矿太阳能电池第41卷　第5期吉林大学学报(信息科学版)Vol.41　No.52023年9月Journal of Jilin University (Information Science Edition)Sept.2023文章编号:1671⁃5896(2023)05⁃0840⁃08电动辅助转向电机控制研究及EMC 设计收稿日期:2022⁃08⁃17作者简介:李任(1998 ),男,江苏徐州人,吉林大学硕士研究生,主要从事EPS 永磁同步电机控制研究,(Tel)86⁃187****7277(E⁃mail)liren19981025@;刘卫平(1978 ),男,长春人,吉林大学教授,主要从事电机控制㊁电动汽车技术研究,(Tel)86⁃133143114911(E⁃mail)liuwp@㊂李　任1,刘卫平1,卢希全1,杨祥卓1,张希明1,刘雪明2,赵　塔2(1.吉林大学仪器科学与电气工程学院,长春130061;2.中车长春轨道客车股份有限公司,国家轨道客车工程研究中心基础研发部,长春130113)摘要:为解决商用车在行驶过程中,传统的液压助力转向系统阻力较大且效率较低,并且在长期使用后保养不当容易泄露,可能引起事故等问题,对电动辅助转向电机控制算法和设计进行了研究㊂电动辅助转向电机选择永磁同步电机,通过应用模糊PID(Proportional Integral Derivative)算法可以精确,快速地调制到参考值㊂同时采用拓展卡尔曼滤波器可以估算永磁同步电机的转子位置,减小控制器的体积及成本㊂在驱动系统中,由于大电流耦合路径多样严重影响电机控制系统的电磁兼容性能,所以电机控制时采用驱动系统EMC(Electro Magnetic Compatibility)设计㊂实验结果表明,基于模糊PID 算法以及拓展卡尔曼滤波器的永磁同步电机控制可以应用于商用车电动辅助转向电机控制中㊂关键词:电动辅助转向;永磁同步电机控制策略;模糊PID 算法;拓展卡尔曼滤波器;EMC 设计中图分类号:TM341;YP273文献标志码:AResearch and EMC Design of Electric Assisted Steering Motor ControlLI Ren 1,LIU Weiping 1,LU Xiquan 1,YANG Xiangzhuo 1,ZHANG Ximing 1,LIU Xueming 2,ZHAO Ta 2(1.College of Instrument Science and Electrical Engineering,Jilin University,Changchun 130061,China;2.National Rail Bus Engineering Research Center Basic Research and Development Department,Crrc Changchun Railway Vehicles Company Limited,Changchun 130113,China)Abstract :In order to solve the problems such as large resistance and low efficiency of the traditional hydraulic power steering system during the driving process of commercial vehicles,improper maintenance after long⁃term use will lead to leakage,and may cause accidents,an electric auxiliary steering motor control is adopted.The electric auxiliary steering motor selects the permanent magnet synchronous motor.By using the fuzzy PID (Proportional Integral Derivative)algorithm,it can be modulated to the reference value accurately and quickly .The extended Kalman filter is used to estimate the rotor position of the permanent magnet synchronous motor,reduce the volume of the controller and reduce the cost.In the drive system,the diversity of large current coupling paths seriously affects the electromagnetic compatibility performance of the motor control system,so the drive system EMC (Electro Magnetic Compatibility)design is adopted.From the experimental results,it isconcluded that the permanent magnet synchronous motor control based on fuzzy PID algorithm and extended Kalman filter can be applied to the electric auxiliary steering motor control of commercial vehicles.Key words :electric auxiliary rotation;control strategy of permanent magnet synchronous motor;fuzzy proportional integral derivative (PID);extended Kalman filter;electro magnetic compatibility (EMC)design 0　引　言转向系统是商务车在行驶过程中,为转动方向以及平稳运行提供的助力控制系统㊂传统的液压助力。

第３９卷第２期２０２０年２月硅㊀酸㊀盐㊀通㊀报ＢＵＬＬＥＴＩＮＯＦＴＨＥＣＨＩＮＥＳＥＣＥＲＡＭＩＣＳＯＣＩＥＴＹＶｏｌ.３９㊀Ｎｏ.２Ｆｅｂｒｕａｒｙꎬ２０２０超高能量电子辐照氮掺杂金刚石的光致发光研究王凯悦１ꎬ常㊀森１ꎬ张文晋１ꎬ郭睿昂１ꎬ田玉明１ꎬ２ꎬ柴跃生１(１.太原科技大学材料科学与工程学院ꎬ太原㊀０３００２４ꎻ２.山西工程职业技术学院ꎬ太原㊀０３０００９)摘要:利用低温光致发光光谱研究了ＭｅＶ超高能量电子辐照氮掺杂金刚石ꎬ结果表明ꎬ辐照缺陷以氮￣空位缺陷(ＮＶ)和中性单空位缺陷(ＧＲ１)为主ꎻ辐照电子经１.２ｍｍ铝箔遮挡后ꎬ其能量大幅度衰减ꎬ金刚石中只剩余了ＮＶ缺陷ꎬ这表明此时辐照产生的空位都被氮杂质所束缚而以ＮＶ缺陷形式存在ꎻ经８００ħ高温退火后ꎬ空位扩散到晶体表面以下约１５μｍ处而被氮杂质束缚ꎬ进而使得ＧＲ１信号减弱而ＮＶ信号增强ꎮ关键词:金刚石ꎻ辐照ꎻ光致发光ꎻ扩散中图分类号:Ｖ２５４.２㊀㊀文献标识码:Ａ㊀㊀文章编号:１００１￣１６２５(２０２０)０２￣０６３９￣０４ＰｈｏｔｏｌｕｍｉｎｅｓｃｅｎｃｅＳｔｕｄｉｅｓｏｎＮｉｔｒｏｇｅｎ￣ＤｏｐｅｄＤｉａｍｏｎｄａｆｔｅｒＵｌｔｒａＨｉｇｈＥｎｅｒｇｙＥｌｅｃｔｒｏｎＩｒｒａｄｉａｔｉｏｎＷＡＮＧＫａｉｙｕｅ１ꎬＣＨＡＮＧＳｅｎ１ꎬＺＨＡＮＧＷｅｎｊｉｎ１ꎬＧＵＯＲｕｉａｎｇ１ꎬＴＩＡＮＹｕｍｉｎｇ１ꎬ２ꎬＣＨＡＩＹｕｅｓｈｅｎｇ１(１.ＳｃｈｏｏｌｏｆＭａｔｅｒｉａｌｓＳｃｉｅｎｃｅａｎｄＥｎｇｉｎｅｅｒｉｎｇꎬＴａｉｙｕａｎＵｎｉｖｅｒｓｉｔｙｏｆＳｃｉｅｎｃｅａｎｄＴｅｃｈｎｏｌｏｇｙꎬＴａｉｙｕａｎ０３００２４ꎬＣｈｉｎａꎻ２.ＳｈａｎｘｉＥｎｇｉｎｅｅｒｉｎｇＶｏｃａｔｉｏｎａｌａｎｄＴｅｃｈｎｉｃａｌＣｏｌｌｅｇｅꎬＴａｉｙｕａｎ０３０００９ꎬＣｈｉｎａ)Ａｂｓｔｒａｃｔ:Ｔｈｅｌｏｗ￣ｔｅｍｐｅｒａｔｕｒｅｐｈｏｔｏｌｕｍｉｎｅｓｃｅｎｃｅｓｐｅｃｔｒｏｓｃｏｐｙｗａｓｅｍｐｌｏｙｅｄｔｏｃｈａｒａｃｔｅｒｉｚｅｔｈｅｎｉｔｒｏｇｅｎ￣ｄｏｐｅｄｄｉａｍｏｎｄｓａｆｔｅｒｕｌｔｒａ￣ｈｉｇｈｅｎｅｒｇｙｅｌｅｃｔｒｏｎｉｒｒａｄｉａｔｉｏｎ.Ｔｈｅｒｅｓｕｌｔｓｓｈｏｗｔｈａｔｔｈｅｉｒｒａｄｉａｔｅｄｄｅｆｅｃｔｓａｒｅｍａｉｎｌｙｎｉｔｒｏｇｅｎ￣ｖａｃａｎｃｙ(ＮＶ)ａｎｄｎｅｕｔｒａｌｓｉｎｇｌｅｖａｃａｎｃｙｄｅｆｅｃｔｓ(ＧＲ１)ꎻａｆｔｅｒｂｅｉｎｇｂｌｏｃｋｅｄｂｙ１.２ｍｍａｌｕｍｉｎｕｍｆｏｉｌꎬｔｈｅｉｒｒａｄｉａｔｉｏｎｅｎｅｒｇｙｉｓｇｒｅａｔｌｙａｔｔｅｎｕａｔｅｄꎬａｎｄｏｎｌｙＮＶｄｅｆｅｃｔｓｒｅｍａｉｎｉｎｄｉａｍｏｎｄ.ＴｈｅｓｅｉｎｄｉｃａｔｅｓｔｈａｔｔｈｅｖａｃａｎｃｉｅｓｇｅｎｅｒａｔｅｄｂｙｉｒｒａｄｉａｔｉｏｎａｒｅｔｒａｐｐｅｄｂｙｎｉｔｒｏｇｅｎｉｍｐｕｒｉｔｉｅｓａｎｄｔｒａｎｓｆｅｒｒｅｄｉｎｔｈｅｆｏｒｍｏｆＮＶｄｅｆｅｃｔｓꎬａｆｔｅｒｈｉｇｈｔｅｍｐｅｒａｔｕｒｅａｎｎｅａｌｉｎｇｏｆ８００ħꎬｔｈｅｖａｃａｎｃｉｅｓｄｉｆｆｕｓｅｆｒｏｍｓｕｒｆａｃｅｔｏｗａｒｄｓｉｎｎｅｒａｂｏｕｔ１５μｍｏｆｔｈｅｃｒｙｓｔａｌꎬａｎｄｔｈｅｎｉｓｔｒａｐｐｅｄｂｙｎｉｔｒｏｇｅｎｉｍｐｕｒｉｔｉｅｓｗｈｉｃｈｌｅａｄｓｉｎｔｏｔｈｅｄｅｃｒｅａｓｅｏｆＧＲ１ｃｅｎｔｅｒｗｈｉｌｅｔｈｅｅｎｈａｎｃｅｍｅｎｔｏｆＮＶｃｅｎｔｅｒ.Ｋｅｙｗｏｒｄｓ:ｄｉａｍｏｎｄꎻｉｒｒａｄｉａｔｉｏｎꎻｐｈｏｔｏｌｕｍｉｎｅｓｃｅｎｃｅꎻｄｉｆｆｕｓｉｏｎ基金项目:国家自然科学基金青年科学基金(６１７０５１７６)ꎻ中国博士后科学基金面上资助(２０１７Ｍ６２０４４９)ꎻ中国博士后科学基金特别资助(２０１８Ｔ１１１０５６)ꎻ陕西省博士后科研资助项目ꎻ陕西省博士后科研项目配套资助ꎻ山西省研究生教育创新项目(２０１８ＳＹ０８６)作者简介:王凯悦(１９８５￣)ꎬ男ꎬ博士ꎬ副教授ꎮ主要从事宽禁带半导体材料研究ꎮＥ￣ｍａｉｌ:ｗａｎｇｋａｉｙｕｅ８＠１６３.ｃｏｍ通讯作者:田玉明ꎬ博士ꎬ教授ꎮＥ￣ｍａｉｌ:ｔｉａｎｙｍｉｎｇ＠１６３.ｃｏｍ０㊀引㊀言金刚石具有宽禁带ꎬ高热导率ꎬ高载流子迁移率和高击穿电压等优点ꎬ使其在光学和电子器件领域有着重要的应用前景ꎬ其性能很大程度上由晶体中的本征缺陷和杂质缺陷所决定[１￣３]ꎬ氮作为金刚石中最常见的杂质原子ꎬ普遍存在于天然和人工合成金刚石中[４￣５]ꎮ对于Ｉｂ型氮掺杂金刚石来说ꎬ其氮原子孤立地分散在整个金刚石晶体的原子阵点位置ꎬ其在电子器件及衬底领域应用非常广泛[６]ꎮ金刚石在晶体生长过程中可形成缺陷ꎬ或者经辐照㊁退火等方法处理后也能形成缺陷ꎮ由于晶体生长过程中晶体缺陷的形成不易操控ꎬ因此目前电子器件常常通过辐照与退火来调控其半导体性能ꎮ中子㊁质子㊁电子㊁α粒子等都成功应用于金刚石的辐照领域ꎬ但其中电子辐照是最为理想的ꎬ它具有能量可控㊁质量小㊁６４０㊀新型功能材料硅酸盐通报㊀㊀㊀㊀㊀㊀第３９卷动能低㊁无引入杂质等优点[７]ꎮ近阈值电子辐照后ꎬ本征缺陷可以成功地引入到纯净的ＩＩａ金刚石中ꎬ并且进一步研究退火引起的本征缺陷扩散性质[８]ꎬ而近来这项技术也被用于氮掺杂和硅掺杂金刚石中[９￣１０]ꎮ然而ꎬ实际的半导体器件通常采用ＭｅＶ超高电子能量进行辐照处理的ꎬ而目前关于Ｉｂ型氮掺杂金刚石高能辐照损伤的研究较少ꎮ因此ꎬ本文利用低温光致发光光谱研究了ＭｅＶ超高能量电子辐照Ｉｂ型氮掺杂金刚石ꎬ这为其半导体性能调控提供了一定的理论依据与技术支持ꎮ１㊀实㊀验实验使用的金刚石样品是高温高压法合成的Ｉｂ型金刚石ꎬ其含氮量高达３００ｐｐｍꎮ金刚石晶体生长是在国产大体积立方高压设备上进行的ꎬ其以高纯度石墨为碳源ꎬ高纯ＦｅＮｉ基合金为触媒ꎬ选择优质金刚石(粒径为０.５~０.７ｍｍ)的(１００)晶面作为初始生长面ꎮ合成参数为５.４ＧＰａ高压和１４５０~１５００ħ生长温度ꎬ合成时间约为６０~６５ｈꎮ然后经沸腾酸洗以除去残留在金刚石表面上的石墨和金属ꎬ再利用激光切割机将其切割成３ｍｍˑ３ｍｍˑ１ｍｍ尺寸ꎬ并将其沿<１００>晶面进行抛光ꎮ将１.２ｍｍ厚的铝箔固定在金刚石上表面上ꎬ以使得金刚石部分被电子辐照ꎮ利用１０ＭｅＶ聚焦电子束辐照整个金刚石晶体３０ｍｉｎꎮ接着利用Ｒｅｎｉｓｈａｗ激光共聚焦显微拉曼光谱仪进行表征ꎬ其光学系统的分辨率为４ｍｍ(水平)和６ｍｍ(垂直)ꎬ且该设备配有Ｌｉｎｋａｍ液氮冷却台ꎬ其测试温度最低可至７７Ｋꎮ所有的光致发光光谱(ＰＬ)都是利用５３２ｎｍ激光器激发在１００Ｋ低温下获得的ꎮ退火实验是在ＲＴ￣１２００快速退火炉氩气氛围中进行的ꎬ退火温度为３００~８００ħꎮ２㊀结果与讨论纯净金刚石的光致发光光谱中只存在Ｒａｍａｎ信号ꎬ其尖锐程度反映了样品的纯度与结晶程度ꎮ而氮掺杂金刚石中最常见的就是氮￣空位缺陷(ＮＶ)ꎬ其在５７５ｎｍ与６３７ｎｍ处存在两个零声子线ꎬ分别对应着中性和负电荷两种ＮＶ缺陷[１１]ꎮ而本实验使用的高温高压Ｉｂ型氮掺杂金刚石中却只观察到了Ｒａｍａｎ峰(见图１(ａ))ꎬ说明此时氮原子是以孤立的形式存在ꎬ而不是以ＮＶ形式存在ꎻ经超高能量电子辐照后ꎬ光谱中出现了ＮＶ中心ꎬ并在６５８ｎｍ处观察到了强的振动结构(见图１(ｂ))ꎻ除此之外ꎬ在７４１ｎｍ处还出现了一个零声子线ꎬ它是由中性单空位引起的ꎬ经常被记作ＧＲ１中心ꎮ在１.２ｍｍ铝箔覆盖区域ꎬ并没有观察到ＧＲ１信号(见图１(ｃ))ꎬ只观察到了很强的ＮＶ－中心ꎮ以上结果表明ꎬ高能电子辐照可在Ｉｂ型金刚石中引入空位缺陷ꎬ并在辐照过程中被杂质氮原子所束缚ꎬ而辐照能量经铝箔衰减后ꎬ在金刚石晶体中引入的空位缺陷数量较少ꎬ这些空位全部被氮原子所束缚以ＮＶ缺陷形式出现ꎮ６１３ｎｍ峰在辐照前后均存在ꎬ我们猜测其是与镍相关的光学中心ꎬ但并未具体证实ꎮ图１㊀氮掺杂金刚石的光致发光光谱Ｆｉｇ.１㊀ＰｈｏｔｏｌｕｍｉｎｅｓｃｅｎｃｅｓｐｅｃｔｒａｏｆＮ￣ｄｏｐｅｄｄｉａｍｏｎｄ利用低温光致发光光谱研究了覆盖铝箔区域与未覆盖铝箔区域经高能电子辐照的变化ꎬ其光致发光信号强度的面扫描结果见图２ꎮ根据ＧＲ１信号的强度分布ꎬ可以区分覆盖铝箔区域与未覆盖铝箔区域ꎮ结果表明ꎬ高能电子辐照后ꎬＧＲ１信号在未覆盖区域较强ꎬ而ＮＶ中心在覆盖铝箔区域较强ꎬ这说明一方面电子辐㊀第２期王凯悦等:超高能量电子辐照氮掺杂金刚石的光致发光研究６４１照后ꎬ形成更多的缺陷中心ꎬ其与ＮＶ中心竞争发光ꎮ二是辐照过程中产生的间隙原子可以与ＮＶ中心的空位发生复合ꎬ从而降低ＮＶ中心的浓度ꎮ随着退火温度的升高ꎬ三个发光信号最初没有显著变化ꎮ当退火温度高于７００ħ时ꎬＧＲ１中心消失ꎬＮＶ－中心有向覆盖区域扩散的趋势ꎬ这说明此时空位已经开始自由移动ꎮ图２㊀辐照和退火后检测区域的面扫描光谱ꎬ扫描步长为１０μｍˑ１０μｍＦｉｇ.２㊀ＰＬｍａｐｐｉｎｇｉｎｔｈｅｄｅｔｅｃｔｉｏｎａｒｅａｓｕｒｆａｃｅａｆｔｅｒｉｒｒａｄｉａｔｉｏｎａｎｄａｎｎｅａｌｉｎｇꎬｔｈｅｓｃａｎｎｉｎｇｓｔｅｐｓｉｓ１０μｍｂｙ１０μｍ使用低温光致发光光谱研究了退火后检测区域的光学中心在深度方向上的分布和迁移ꎮ图３是检测区域的３Ｄ面扫描光谱ꎮ由图中可以看出ꎬ不同中心的深度分布之间存在差异ꎮ电子辐照后ꎬＮＶ中心主要分布在覆盖铝箔的区域ꎬ而ＧＲ１则集中分布在未覆盖区域中(为便于观察ꎬ将ＧＲ１的３Ｄ面扫描光谱水平旋转１８０ʎ)ꎮ这与之前讨论的结果一致ꎮ点缺陷的分布在远离分界线处最强ꎮ由于入射电子具有极强的能量ꎬ在２０μｍ表面下也产生一定数量的点缺陷ꎬ随着深度的增加ꎬ强度逐渐减弱ꎮ图３㊀在５３２ｎｍ激发波长和约１００Ｋ下获得的辐照和退火后检测区域中的３Ｄ面扫描光谱ꎬ检测深度为５０~１２０μｍＦｉｇ.３㊀３ＤＰＬｍａｐｐｉｎｇｉｎｔｈｅｄｅｔｅｃｔｉｏｎａｒｅａａｆｔｅｒｉｒｒａｄｉａｔｉｏｎａｎｄａｎｎｅａｌｉｎｇｏｂｔａｉｎｅｄａｔ５３２ｎｍｅｘｃｉｔａｔｉｏｎａｎｄａｂｏｕｔ１００Ｋꎬｔｈｅｄｅｐｔｈｏｆｄｅｔｅｃｔｉｏｎｉｓ５０￣１２０μｍ在４００ħ退火后ꎬ空位不仅在横向上移动ꎬ而且在深度方向上显著扩散ꎮＧＲ１中心尤为明显ꎮ有趣的是ꎬ光学中心的发光似乎是沿着各自的方向向下扩散ꎮＮＶ发光在铝箔覆盖的区域向下扩散ꎬ而ＧＲ１在未覆６４２㊀新型功能材料硅酸盐通报㊀㊀㊀㊀㊀㊀第３９卷盖区域沿深度方向扩散ꎮ在８００ħ退火后ꎬ空位扩散明显ꎮ对于ＮＶ中心ꎬ最高强度移动至表面以下ꎮ在金刚石表面附近几乎观察不到ＮＶ中心ꎬ但可以在表面以下约１５μｍ处观察到它的高强度ꎮＧＲ１信号消失了ꎮ随着退火温度的升高ꎬ拉曼信号减弱ꎮ在５００~８００ħ退火后ꎬＧＲ１逐渐减弱直至消失ꎻ而ＮＶ中心则得到了增强ꎮ这是因为当退火温度达到７００ħ时空位可以自由移动ꎬ并且大量的取代氮原子可以结合这些移动的空位以形成ＮＶ中心ꎮ３㊀结㊀论氮掺杂金刚石经超高能量电子辐照后ꎬ晶体中形成了ＮＶ与Ｖ０缺陷ꎻ辐照能量经铝箔衰减后ꎬ辐照产生的空位数量减少而被杂质氮原子全部束缚ꎬ经高温退火后ꎬ空位扩散至晶体表面以下约１５μｍ处ꎬ而被杂质氮所束缚ꎬ使得ＧＲ１信号减弱而ＮＶ信号增强ꎮ参考文献[１]㊀王凯悦ꎬ李志宏ꎬ田玉明ꎬ等.金刚石中ＧＲ１中心的光致发光特性研究[Ｊ].物理学报ꎬ２０１３ꎬ６２(６):４１９￣４２３.[２]㊀ＳｃｈｗａｎｄｅｒＭꎬＰａｒｔｅｓＫ.ＡｒｅｖｉｅｗｏｆｄｉａｍｏｎｄｓｙｎｔｈｅｓｉｓｂｙＣＶＤｐｒｏｃｅｓｓｅｓ[Ｊ].ＤｉａｍｏｎｄａｎｄＲｅｌａｔｅｄＭａｔｅｒｉａｌｓꎬ２０１１ꎬ２０:１２８７￣１３０１. [３]㊀ＭａｉｄａＯꎬＨｏｒｉＴꎬＫｏｄａｍａＴꎬｅｔａｌ.Ｃｈａｒａｃｔｅｒｉｚａｔｉｏｎｏｆｄｅｅｐｄｅｆｅｃｔｓｉｎｂｏｒｏｎ￣ｄｏｐｅｄＣＶＤｄｉａｍｏｎｄｆｉｌｍｓｕｓｉｎｇｔｒａｎｓｉｅｎｔｐｈｏｔｏｃａｐａｃｉｔａｎｃｅｍｅｔｈｏｄ[Ｊ].ＭａｔｅｒｉａｌｓＳｃｉｅｎｃｅｉｎＳｅｍｉｃｏｎｄｕｃｔｏｒＰｒｏｃｅｓｓｉｎｇꎬ２０１７ꎬ７０:２０３￣２０６.[４]㊀李尚升ꎬ许安涛ꎬ王生艳ꎬ等.Ｎ型半导体金刚石的研究现状与展望[Ｊ].人工晶体学报ꎬ２０１６ꎬ４５(１１):２７２８￣２７３４＋２７４０.[５]㊀ＷａｎｇＫＹꎬＳｔｅｅｄｓＪＷꎬＬｉＺＨꎬｅｔａｌ.Ｐｈｏｔｏｌｕｍｉｎｅｓｃｅｎｃｅｓｔｕｄｉｅｓｏｆｇｒｏｗｔｈ￣ｓｅｃｔｏｒｄｅｐｅｎｄｅｎｃｅｏｆｎｉｔｒｏｇｅｎｄｉｓｔｒｉｂｕｔｉｏｎｉｎｓｙｎｔｈｅｔｉｃＩｂｄｉａｍｏｎｄ[Ｊ].ＭａｔｅｒｉａｌｓＣｈａｒａｃｔｅｒｉｚａｔｉｏｎꎬ２０１４ꎬ９４:１４￣１８.[６]㊀ＭａｔｓｕｍｏｔｏＴꎬＭｕｋｏｓｅＴꎬＭａｋｉｎｏＴꎬｅｔａｌ.ＤｉａｍｏｎｄＳｃｈｏｔｔｋｙ￣ｐｎｄｉｏｄｅｕｓｉｎｇｌｉｇｈｔｌｙｎｉｔｒｏｇｅｎ￣ｄｏｐｅｄｌａｙｅｒ[Ｊ].ＤｉａｍｏｎｄａｎｄＲｅｌａｔｅｄＭａｔｅｒｉａｌｓꎬ２０１７ꎬ７５:１５２￣１５４.[７]㊀王凯悦.光致发光光谱研究电子辐照金刚石的光学中心[Ｄ].天津:天津大学ꎬ２０１２.[８]㊀ＷａｎｇＫＹꎬＳｔｅｅｄｓＪＷꎬＬｉＺＨꎬｅｔａｌ.ＡｎｎｅａｌｉｎｇａｎｄｌａｔｅｒａｌｍｉｇｒａｔｉｏｎｏｆｄｅｆｅｃｔｓｉｎＩＩａｄｉａｍｏｎｄｃｒｅａｔｅｄｂｙｎｅａｒ￣ｔｈｒｅｓｈｏｌｄｅｌｅｃｔｒｏｎｉｒｒａｄｉａｔｉｏｎ[Ｊ].ＡｐｐｌｉｅｄＰｈｙｓｉｃｓＬｅｔｔｅｒｓꎬ２０１７ꎬ１１０(１５):１５２１０１.[９]㊀ＳｔｅｅｄｓＪＷꎬＫｏｈｎＳ.ＡｎｎｅａｌｉｎｇｏｆｅｌｅｃｔｒｏｎｒａｄｉａｔｉｏｎｄａｍａｇｅｉｎａｗｉｄｅｒａｎｇｅｏｆＩｂａｎｄＩＩａｄｉａｍｏｎｄｓａｍｐｌｅｓ[Ｊ].ＤｉａｍｏｎｄａｎｄＲｅｌａｔｅｄＭａｔｅｒｉａｌｓꎬ２０１４ꎬ５０:１１０￣１２２.[１０]㊀ＷａｎｇＫＹꎬＤｉｎｇＳＣꎬＺｈａｎｇＹＦꎬｅｔａｌ.ＣｒｅａｔｉｏｎａｎｄｍｉｇｒａｔｉｏｎｏｆｉｎｔｒｉｎｓｉｃｄｅｆｅｃｔｓｉｎＳｉ￣ｄｏｐｅｄｄｉａｍｏｎｄｐｒｏｄｕｃｅｄｕｓｉｎｇｍｉｃｒｏｗａｖｅｐｌａｓｍａｃｈｅｍｉｃａｌｖａｐｏｒｄｅｐｏｓｉｔｉｏｎ[Ｊ].ＰｈｙｓｉｃａＳｔａｔｕｓＳｏｌｉｄｉＡꎬ２０１９ꎬ２１６(１１):１９００００３.[１１]㊀ＤｏｈｅｒｔｙＭＷꎬＭａｎｓｏｎＮＢꎬＤｅｌａｎｅｙＰꎬｅｔａｌ.Ｔｈｅｎｉｔｒｏｇｅｎ￣ｖａｃａｎｃｙｃｏｌｏｕｒｃｅｎｔｒｅｉｎｄｉａｍｏｎｄ[Ｊ].ＰｈｙｓｉｃｓＲｅｐｏｒｔｓꎬ２０１３ꎬ５２８(１):１￣４５.。

收稿日期：2020⁃09⁃29。

收修改稿日期：2020⁃12⁃28。

国家自然科学基金(No.21875037，51502036)和国家重点研发计划(No.2016YFB0302303，2019YFC1908203)资助。

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E⁃mail ：***************.cn ，***************第37卷第3期2021年3月Vol.37No.3509⁃515无机化学学报CHINESE JOURNAL OF INORGANIC CHEMISTRYp 区金属氧化物Ga 2O 3和Sb 2O 3光催化降解盐酸四环素性能差异毛婧芸1黄毅玮2黄祝泉1刘欣萍1薛珲＊,1肖荔人＊,3(1福建师范大学环境科学与工程学院，福州350007)(2福建师范大学生命科学学院，福州350007)(3福建师范大学化学与材料学院，福州350007)摘要：对沉淀法合成的p 区金属氧化物Ga 2O 3和Sb 2O 3紫外光光催化降解盐酸四环素的性能进行了研究，讨论了制备条件对光催化性能的影响。

最佳制备条件下得到的Ga 2O 3⁃900和Sb 2O 3⁃500样品光催化性能存在巨大差异，通过X 射线粉末衍射、傅里叶红外光谱、N 2吸附-脱附测试、荧光光谱、拉曼光谱、电化学分析及活性物种捕获实验等对样品进行分析，研究二者光催化降解盐酸四环素的机理，揭示影响光催化性能差异的本质因素。

结果表明，Ga 2O 3和Sb 2O 3光催化性能差异主要归结于二者不同的电子和晶体结构、表面所含羟基数量及光催化降解机理。

关键词：p 区金属；氧化镓；氧化锑；光催化；盐酸四环素中图分类号：O643.36；O614.37+1；O614.53+1文献标识码：A文章编号：1001⁃4861(2021)03⁃0509⁃07DOI ：10.11862/CJIC.2021.063Different Photocatalytic Performances for Tetracycline Hydrochloride Degradation of p ‑Block Metal Oxides Ga 2O 3and Sb 2O 3MAO Jing⁃Yun 1HUANG Yi⁃Wei 2HUANG Zhu⁃Quan 1LIU Xin⁃Ping 1XUE Hun ＊,1XIAO Li⁃Ren ＊,3(1College of Environmental Science and Engineering,Fujian Normal University,Fuzhou 350007,China )(2College of Life and Science,Fujian Normal University,Fuzhou 350007,China )(3College of Chemistry and Materials Science,Fujian Normal University,Fuzhou 350007,China )Abstract:The UV light photocatalytic performances of p ⁃block metal oxides Ga 2O 3and Sb 2O 3synthesized by a pre⁃cipitation method for the degradation of tetracycline hydrochloride were explored.The effects of synthesis conditions on the photocatalytic activity were discussed.The Ga 2O 3⁃900and Sb 2O 3⁃500samples prepared under optimal condi⁃tions exhibited a remarkable photocatalytic activity difference,which were characterized by X⁃ray diffraction,Fouri⁃er transform infrared spectroscopy,N 2adsorption⁃desorption tests,fluorescence spectrum,Raman spectrum,electro⁃chemical analysis and trapping experiment of active species.The photocatalytic degradation mechanisms of tetracy⁃cline hydrochloride over the photocatalysts were proposed and the essential factors influencing the difference of pho⁃tocatalytic performance were revealed.The results show that the different photocatalytic activities observed for Ga 2O 3and Sb 2O 3can be attributed to their different electronic and crystal structures,the amount of hydroxyl groupin the surface and the photocatalytic degradation mechanisms.Keywords:p ⁃block metal;Ga 2O 3;Sb 2O 3;photocatalysis;tetracycline hydrochloride无机化学学报第37卷0引言盐酸四环素(TC)作为一种四环素类广谱抗生素，被广泛应用于治疗人体疾病及预防畜禽、水产品的细菌性病害，其在世界范围的大量使用致使其在环境中积累[1]。

山　东　化　工 收稿日期：２０２０－１２－２７基金项目：湖南中医药管理局“一般项目”项目名称：“元胡止痛亲水凝胶缓释片的研制”（ＮＯ．２０１８８３）作者简介：唐婷（１９８８—），女，湖南株洲人，硕士，讲师，研究方向：中药制剂学。

元胡止痛亲水凝胶缓释片稳定性研究唐婷，陈双华，汤文婷，文芳（湖南中医药高等专科学校，湖南株洲　４１２０００）摘要：目的：以元胡止痛亲水凝胶缓释片中延胡索的累积溶出百分率为指标，采用强化实验（高温、高湿、强光）等影响因素对元胡止痛缓释片的稳定性进行考察，探究其贮藏方式。

方法：以延胡索乙素的累积溶出百分率及含量为指标，在高温、高湿、强光等影响因素下，考察各个因素对元胡止痛亲水凝胶骨架片稳定性的影响。

结果：与０ｄ比较，高温、强光对元胡止痛亲水凝胶缓释片各项指标影响基本不大，但在高湿条件下，增加了缓释片的重量，但对其溶出度及含量影响并无差异。

结论：元胡止痛亲水凝胶缓释片应密闭进行贮藏，防止受潮。

关键词：元胡止痛；亲水凝胶；缓释中图分类号：Ｒ９４４．４ 文献标识码：Ａ 文章编号：１００８－０２１Ｘ（２０２１）０６－０００４－０３ＳｔｕｄｙｏｎｔｈｅＳｔａｂｉｌｉｔｙｏｆＹｕａｎｈｕｚｈｉｔｏｎｇＨｙｄｒｏｐｈｉｌｉｃＧｅｌＳｕｓｔａｉｎｅｄＲｅｌｅａｓｅＴａｂｌｅｔｓＴａｎｇＴｉｎｇ，ＣｈｅｎＳｈｕａｎｇｈｕａ，ＴａｎｇＷｅｎｔｉｎｇ，ＷｅｎＦａｎｇ（ＨｕｎａｎｔｒａｄｉｔｉｏｎａｌＣｈｉｎｅｓｅＭｅｄｉｃｉｎｅＣｏｌｌｅｇｅ，Ｈｕｎａｎ　４１２０００，Ｃｈｉｎａ）Ａｂｓｔｒａｃｔ：Ｏｂｊｅｃｔｉｖｅ：ＴｏｉｎｖｅｓｔｉｇａｔｅｔｈｅｓｔａｂｉｌｉｔｙｏｆＹｕａｎｈｕｚｈｉｔｏｎｇｓｕｓｔａｉｎｅｄｒｅｌｅａｓｅｔａｂｌｅｔｓａｎｄｅｘｐｌｏｒｅｔｈｅｉｒｓｔｏｒａｇｅｍｅｔｈｏｄｓｂｙｔａｋｉｎｇｔｈｅｃｕｍｕｌａｔｉｖｅｄｉｓｓｏｌｕｔｉｏｎｐｅｒｃｅｎｔａｇｅｏｆＹａｎｈｕｚｈｉｔｏｎｇｆｒｏｍｙｕａｎｈｕｚｈｉｔｏｎｇｈｙｄｒｏｐｈｉｌｉｃｇｅｌｔａｂｌｅｔｓａｓｔｈｅｉｎｄｅｘａｎｄｕｓｉｎｇｅｎｈａｎｃｅｄｅｘｐｅｒｉｍｅｎｔｓ（ｈｉｇｈｔｅｍｐｅｒａｔｕｒｅ，ｈｉｇｈｈｕｍｉｄｉｔｙ，ｓｔｒｏｎｇｌｉｇｈｔ）ａｎｄｏｔｈｅｒｉｎｆｌｕｅｎｃｉｎｇｆａｃｔｏｒｓ．Ｍｅｔｈｏｄｓ：Ｕｎｄｅｒｔｈｅｉｎｆｌｕｅｎｃｅｏｆｈｉｇｈｔｅｍｐｅｒａｔｕｒｅ，ｈｉｇｈｈｕｍｉｄｉｔｙａｎｄｓｔｒｏｎｇｌｉｇｈｔ，ｔｈｅｃｕｍｕｌａｔｉｖｅｄｉｓｓｏｌｕｔｉｏｎｐｅｒｃｅｎｔａｇｅａｎｄｃｏｎｔｅｎｔｏｆＴｅｔｒａｈｙｄｒｏｐｈｉｌｉｃｒｈｉｚｏｍａｃｏｒｙｄａｌｉｓｗｅｒｅｕｓｅｄａｓｉｎｄｅｘｅｓｔｏｉｎｖｅｓｔｉｇａｔｅｔｈｅｉｎｆｌｕｅｎｃｅｏｆｖａｒｉｏｕｓｆａｃｔｏｒｓｏｎｔｈｅｓｔａｂｉｌｉｔｙｏｆｙｕａｎｈｕｚｈｉｔｏｎｇｈｙｄｒｏｐｈｉｌｉｃｇｅｌｍａｔｒｉｘｔａｂｌｅｔｓ．Ｒｅｓｕｌｔｓ：Ｃｏｍｐａｒｅｄｗｉｔｈ０ｄａｙｓ，ｈｉｇｈｔｅｍｐｅｒａｔｕｒｅａｎｄｓｔｒｏｎｇｌｉｇｈｔｈａｄｌｉｔｔｌｅｅｆｆｅｃｔｏｎｖａｒｉｏｕｓｉｎｄｅｘｅｓｏｆｙｕａｎｈｕｚｈｉｔｏｎｇｈｙｄｒｏｐｈｉｌｉｃｈｙｄｒｏｇｅｌｓｕｓｔａｉｎｅｄｒｅｌｅａｓｅｔａｂｌｅｔｓ，ｂｕｔｕｎｄｅｒｈｉｇｈｈｕｍｉｄｉｔｙｃｏｎｄｉｔｉｏｎｓ，ｔｈｅｗｅｉｇｈｔｏｆｔｈｅｓｕｓｔａｉｎｅｄｒｅｌｅａｓｅｔａｂｌｅｔｓｗａｓｉｎｃｒｅａｓｅｄ，ｂｕｔｔｈｅｄｉｓｓｏｌｕｔｉｏｎａｎｄｃｏｎｔｅｎｔｏｆｔｈｅｔａｂｌｅｔｓｗｅｒｅｎｏｔｄｉｆｆｅｒｅｎｔ．Ｃｏｎｃｌｕｓｉｏｎ：Ｙｕａｎｈｕｚｈｉｔｏｎｇｈｙｄｒｏｐｈｉｌｉｃｇｅｌｓｕｓｔａｉｎｅｄｒｅｌｅａｓｅｔａｂｌｅｔｓｓｈｏｕｌｄｂｅｓｔｏｒｅｄｉｎａｓｅａｌｅｄｃｏｎｔａｉｎｅｒｔｏｐｒｅｖｅｎｔｍｏｉｓｔｕｒｅｅｘｐｏｓｕｒｅ．Ｋｅｙｗｏｒｄｓ：Ｙｕａｎｈｕｚｈｉｔｏｎｇ；ｈｙｄｒｏｐｈｉｌｉｃｇｅｌ；ｓｕｓｔａｉｎｅｄｒｅｌｅａｓｅｔａｂｌｅｔｓ 元胡止痛方是名方，它由醋制元胡索及白芷两味药构成，具有理气、活血、止痛等作用［１］。