Structure Characterization of HSQ Films for Low Dielectrics Using D5 as Sacrificial Porous

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CHIN.PHYS.LETT.Vol.24,No.12(2007)3532 Structure Characterization of HSQ Films for Low Dielectrics Using D5asSacrificial Porous Materials∗YIN Gui-Qin( )∗∗,NING Zhao-Yuan( ),YUAN Qiang-Hua( )Department of Physics,Soochow University,Suzhou215006(Received3May2007)Low-density materials,commercially available hydrogensilsesquioxane(HSQ)offer a low dielectric constant.HSQ films can be obtained by spin on deposition(SOD).In this work,low-dielectric-constant HSQfilms are prepared by using D5(decamethylcyclopentasiloxane)as sacrificial porous materials.The dielectric constant of silicafilms significantly changes from3.0to2.4.We report the structural aspects of thefilms in relation to their composition after annealed at300◦C,400◦C,and500◦C for1.5h in nitrogen ambient and annealed at400◦C for1.5h in vacuum.Si–OH appears after annealed at400◦C for1.5h in vacuum.The results indicate that the proper condition is in nitrogen ambient.Intensity of the Si–H peak increases with the increasing temperature.Fourier transform infrared spectroscopy is used to identify the network structure and cage structure of Si–O–Si bonds and other possible bonds.Dielectric constant k is significantly lowered by annealing at350◦C for1.5h in nitrogen ambient.The I–V and C–V measurements are used to determine the dielectric constant,the electric resistivity and the breakdown electricfield.PACS:77.84.−s,81.20.Fw,81.15.Rs.Low dielectric constant(low-k)material is one of the central development targets in the electronics in-dustry.For example,microchip device densities con-tinue to increase,generating much demands for insu-lators with a lower dielectric constant than that of dense silicon dioxide(k=3.9−4.2).According to the international technology roadmap for semiconductors (ITRS),it is necessary to obtain thefilm with the lower dielectric constant and high conductivity metal for interconnects in order to reduce this delay and to increase the signal propagation speed.[1−3]Reducing the dielectric constant of afilm can be accomplished either by introduction of pores or by reducing the po-larization of chemical bonds.Many deposition tech-niques have been reported to fabricate porous low-k materials.Spin-on deposition(SOD)is a very poten-tial method because pore volume and pore size can be controlled at the chemical solution stage.Dielectric constant materials presently under investigation are MSQ,HSQ,SiCOH,porous silica and silica-carbon andfluorinated-carbon.[4−6]Among various low-k ma-terials,hydrogensilsesquioxane(HSQ)is one of the promising candidates at65nm technology.The low-k property of HSQ can be achieved by maximized the density of Si–H bonds and minimized the Si–OH bonds.HSQ is a high porous three-dimensional net-work structure,which has a low dielectric constant. The low-k materials must have high quality and re-liability,prepared by a simple process,and should be compatible to different processes employed during integration.[7]In this Letter,we focus on porous organic silicon by decomposing the sacrificial materials within the HSQfilms.This method has the advantage of high porosities and using homogeneous precursors to bet-ter control over composition and decomposition.We report the ordered hybrid porousfilms by using D5 (decamethylcyclopentasiloxane)and the structure of thesefilms annealed at300◦C,400◦C,and500◦C for 1.5h in nitrogen ambient and annealed at400◦C for 1.5h in vacuum.We took10mL HSQ and2mL D5solved in3mL methyl isobutyl ketone(MIBK)and stirred for20min by using magnetic stick.The P-Si(100)wafers cleaned by the standard RCA are spin-coated with this mix-ing of HSQ and D5and then baked on the hot plate at300◦C for1min.They are followed by furnace annealing at300◦C,400◦C and500◦C for1.5h in ni-trogen ambient and at400◦C for1.5h in vacuum.An untreated sample(without any post-treatment)was used as the reference.Thefilms thicknesses were measured by an ET350 profilometer.Thefilm chemical bonding and struc-ture were characterized by FTIR spectroscopy using a JASCO600Plus with4cm−1resolution.The dielec-tric constant k was extracted from the capacitance-voltage(C−V)characteristics measured at1MHz frequency by HP4294A.The C−V characteristics and the current-voltage(I−V)measurements by Keith-ley6517A were performed on MIS structures fabri-cated as Aluminum/MSQ/p-Si.The current-voltage (I−V)characteristics of these MIS structures were also measured to evaluate the leakage current.The FTIR spectrum of HSQ gives the following∗Support by the National Natural Science Foundation of China under Grant No10575074,and the Specialized Research Fund for the Doctoral Programme of Higher Education of China under Grant No20050285007.∗∗Email:yinguiq@c 2007Chinese Physical Society and IOP Publishing LtdNo.12YIN Gui-Qin et al.3533absorption peaks:(1)Si–H stretch mode (2250cm −1),(2)Si-O stretch cage-like peak (1130cm −1),(3)Si-O stretch network (1070cm −1),(4)Si-O bending net-work peak (860cm −1),(5)Si-O bending network peak (830cm −1).Fig.1.Structure of D5liquid.Figure 1shows the network structure of D5.Fig-ure 2shows the FTIR spectra of HSQ adding D5films with (a)annealed at 300◦C for 1.5h in N 2,(b)an-nealed at 400◦C for 1.5h in vacuum,(c)annealed at 500◦C for 1.5h in N 2,(d)untreated,(e)annealed at 400◦C for 1.5h in N 2.The results indicate that the intensity of Si–H (2250cm −1)stretch bonds at 500◦C is stronger than those at 400◦C and 300◦C.Thus it is good to keep Si–H bonds for low-k materials at higher annealing temperature.The Si–OH (about 3670cm −1)bonds appear after annealing at 400◦C in vacuum.The possible reason is that Si–CH 3(about 1260cm −1)bonds and C–H (about 2960cm −1)bonds were broken during the annealing,and then they form Si–OH bonds.Si–OH bonds correspond to moisture.The highly orientation polarized Si–OH components will increase the k value of the films.Furthermore,the Si–OH bonds in the HSQ films lead to moisture uptake,which is responsible for increases of the k value and the leakage current density.[8]These results indi-cate that films annealed in vacuum can not eliminate absorbed water,so the proper condition is in nitrogen ambient.Peak intensity of the Si–O cage-like struc-ture was less than that of the Si-O network structure shown in Fig.2(d).After annealed,the intensity of Si-O cage-like structure became stronger than without annealed.As we all know,the Si–O cage-like structure has low molecular density.Thus it is benefit to low-k materials.Therefore,annealing is necessary to keep Si–H bonds and Si–O cage-like structure.Fig.2(c)is similar to HSQ,which only has Si–H bond and Si–O–Si bonds.These show that D5has been decomposed after annealed,which can produce porosities in the HSQ films.The dielectric constant is calculated by the stan-dard expression k =Cd/ε0A,where C is the capaci-tance,d is the thickness of the film,ε0is the permittiv-ity (8.854×10−12Fm −1),and A is the electrode area.The thicknesses of these films are conducted by an ET350profilometer,which are (a)285nm,(b)283nm,(c)282nm,(d)281nm.Figure 3shows the dielectric constant of the HSQ films adding D5films with (a)un-treated,(b)annealed at 300◦C for 1.5h in N 2,(c)an-nealed at 400◦C for 1.5h in N 2,(d)annealed at 500◦C for 1.5h in N 2.The dielectric constant decreases after annealing.The structure of annealed films have been changed,e.g.,the absorbed water bonds (Si–OH)de-crease and the cage-like structure Si–O–Si bonds in-crease,which result in decrease of dielectric constant.The dielectric constant increases with increasing tem-perature.The reason is that the network structure Si–O–Si bonds increases with the increasing anneal-ing temperature,which result in increase of moleculardensity.Fig.2.FTIR spectra of HSQ adding D5films (a )an-nealed at 300◦C for 1.5h in N 2,annealed at 300◦C for 1.5h in N 2,(b )annealed at 400◦C for 1.5h in vacuum,(c )annealed at 500◦C for 1.5h in N 2,(d )untreated,(e )annealed at 400◦C for 1.5h in N 2.Fig.3.Dielectric constant of HSQ films (a)untreated,(b)annealed at 300◦C for 1.5h in N 2,(c)annealed at 400◦C for 1.5h in N 2,(d)annealed at 500◦C for 1.5h in N 2.Figure 4shows the leakage current density of HSQ films (a)annealed at 300◦C for 1.5h in N 2;(b)an-3534YIN Gui-Qin et al.Vol.24nealed at 400◦C for 1.5h in N 2;(c)annealed at 500◦C for 1.5h in N 2.The leakage current density in Fig.4(c)is less than the others.The same reason is that Si–OH disappears and molecular density increases.The leak-age current density in Fig.4(b)increases no less than one magnitude compared to the others.The reason is that at 400◦C,the intensity of the cage-like structure Si–O–Si bonds is higher than those at 500◦C and at 300◦C.Fig.4.Leakage current density of HSQ films (a)annealed at 300◦C for 1.5h in N 2,(b)annealed at 400◦C for 1.5h in N 2,(c)annealed at 500◦C for 1.5h in N 2.In summary,we have shown the structure of the HSQ films annealed at 300◦C,400◦C,and 500◦C for 1.5h in nitrogen ambient and annealed at 400◦C for 1.5h in vacuum by using D5(decamethylcyclopen-tasiloxane)as sacrificial porous materials.The results indicate that the proper annealing condition is in ni-trogen ambient.In nitrogen ambient,the cage-like structure Si–O–Si bonds increase and absorbed wa-ter bonds (Si–OH)decrease,leading to low dielectric constant of the films.The reason is that the charac-teristic of nitrogen is very stable,so it is the structural change of these films to lower the dielectric constant.We have also shown that the leakage current density and dielectric constant both can be improved after annealing in nitrogen ambient.The leakage current density decreases with the increasing annealing tem-perature.References[1]Seidel T E and Ting C H 1995Mater.Res.Soc.Symp.Proc.3813[2]Pai P L and Ting C H 1989Proc.IEEE VIMC Conference(Santo 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