高温退火处理下SiNx薄膜组成及键合结构变化

采用等离子增强化学气相沉积法, 以氨气和硅烷为反应气体, p型单晶硅为衬底, 低温下(200 ℃)制备了非化学计量比氮化硅(SiN_x)薄膜. 在N₂氛围中, 于500–1100 ℃范围内对薄膜进行热退火处理. 室温下分别使用Fourier变换红外吸收(FTIR)光谱技术和X射线光电子能谱(XPS)技术测量未退火以及退火处理后SiN_x薄膜的Si–N, Si–H, N–H键键合结构和Si 2p, N 1s电子结合能以及薄膜内N和Si原子含量比值R的变化. 详细讨论了不同温度退火处理下SiN_x薄膜的FTIR和XPS光谱演化同薄膜内Si, N, H原子间键合方式变化之间的关系. 通过分析FTIR和XPS光谱发现退火温度低于800 ℃时, SiN_x薄膜内Si–H和N–H键断裂后主要形成Si–N键; 当退火温度高于800 ℃时薄膜内Si–H和N–H键断裂利于N元素逸出和Si纳米粒子的形成; 当退火温度达到1100 ℃时N₂与SiN_x薄膜产生化学反应导致薄膜内N和Si原子含量比值R增加. 这些结果有助于控制高温下SiN_x薄膜可能产生的化学反应和优化SiN_x薄膜内的Si纳米粒子制备参数. 关键词： x薄膜')" href="#">SiN_x薄膜 Fourier变换红外吸收光谱 X射线光电子能谱 键合结构     

氮化硅介质中双层纳米硅薄膜的两级电荷存储

研究镶嵌在超薄非晶氮化硅(a-SiN_x)层之间的双层纳米硅(nc-Si)的电荷存储现象.利用等离子体增强化学气相淀积(PECVD)技术在硅衬底上制备a-SiN_x/a-Si/a-SiN_x/a-Si/a-SiN_x多层薄膜结构.采用常规热退火方法使非晶硅(a-Si)层晶化，形成包含双层nc-Si的金属-氮化物-半导体(MIS)结构.通过电容电压(C-V)特性测量，观测到该结构中由于电荷存储引起的C-V回滞现象，并在室温下成功观察到载流子基于Fowler-Nordheim(F-N)隧穿注入到第一层、第二层nc-Si的两级电荷存储状态.结合电流电压(I-V)特性的测量，对电荷存储的机理进行了深入分析. 关键词： 纳米硅 氮化硅 电容电压法 电流电压法     

The charge storage of the nc—Si layer

Sandwiched structures (a-SiN_x/a-Si/a-SiN_x) have been fabricated by the plasma enhanced chemical vapour deposition technique. A Si nanocrystal (nc-Si) layer was formed by crystallization of an a-Si layer according to the constrained crystallization principle after quasi-static thermal annealing at 1100℃ for 30 min. Transmission electron microscopy (TEM) and Raman scattering spectroscopy clearly demonstrated that nc-Si grains were formed in the as-deposited a-Si layer after annealing. The density of nc-Si grains is about 10¹¹cm^-2 as shown by TEM photographs. Using capacitance－voltage (C－V) measurements we investigated the electrical characteristics of the sandwiched structures. The charge storage phenomenon of the nc-Si layer was observed from the shift of flat-band voltage (V_FB) in C－V curves at a high frequency (1 MHz). We estimated the density of nc-Si grains to be about 10¹¹cm^-2 from the shift value of V_FB, which is in agreement with the result of TEM photographs. At the same time, we found that the shift of V_FB increased with the increase of the applied constant dc voltage or the thickness of the nc-Si layer.     

Amorphous Si/insulator multilayers grown by vacuum deposition and electron cyclotron resonance plasma treatment

a-Si/insulator multilayers have been deposited on (0 0 1) Si by electron gun Si evaporation and periodic electron cyclotron resonance plasma oxidation or nitridation. Exposure to an O or N plasma resulted in the formation of a thin SiO₂ and SiN_x layer whose thickness was self-limited and controlled by process parameters. For thin-layer (2 nm) Si/SiO₂ and Si/SiN_x multilayers no visible photoluminescence (PL) was observed in most samples, although all exhibited weak “blue” PL. For the nitride multilayers, annealing at 750°C or 850°C induced visible PL that varied in peak energy with Si layer thickness. Depth profiling of a-Si caps on thin insulating layers revealed no detectable contamination for the SiN_x layers, but substantial O contamination for the SiO₂ films.     

后退火增强氢化非晶硅钝化效果的研究

在本征氢化非晶硅(a-Si:H(i))/晶体硅(c-Si)/a-Si:H(i)异质结构上溅射ITO时, 发现后退火可大幅增加ITO/a-Si:H(i)/c-Si/a-Si:H(i)的少子寿命(从1.7 ms到4 ms). 这一增强效应可能的三个原因是: ITO/a-Si:H(i)界面场效应作用、退火形成的表面反应层影响以及退火对a-Si:H(i)材料本身的优化, 但本文研究结果表明少子寿命增强效应与ITO和表面反应层无关; 对不同沉积温度制备的a-Si:H(i)/c-Si/a-Si:H(i)异质结后退火的研究表明: 较低的沉积温度(<175 ℃)后退火增强效应显著, 而较高的沉积温度(>200 ℃)后退火增强效应不明显, 可以确定“低温长高温后退火”是获得高质量钝化效果的一种有效方式; 采用傅里叶红外吸收谱(FTIR)研究不同沉积温度退火前后a-Si:H(i)材料本身的化学键构造, 发现退火后异质结少子寿命大幅提升是由于a-Si:H(i)材料本身的结构优化造成的, 其深层次的本质是通过材料的生长温度和退火温度的优化匹配来控制包括H含量、H键合情况以及Si原子无序性程度等微观因素主导作用的一种竞争性平衡, 对这一平衡点的最佳控制是少子寿命大幅提升的本质原因.     

a-Si ∶H/SiO2多量子阱材料制备及其光学性能和微结构研究

利用等离子体增强化学气相沉积技术制备了a-Si ∶H/SiO₂多量子阱结构材料.对a-Si ∶H/SiO₂多量子阱样品分别进行了3种不同的热处理,其中样品经1100 ℃高温退火可获得尺寸可控的nc-Si:H/SiO₂量子点超晶格结构,其尺寸与非晶硅子层厚度相当.比较了a-Si ∶H/SiO₂多量子阱材料与相同制备工艺条件下a-Si ∶H材料的吸收系数,在紫外/可见短波段前者的吸收系数明显增大,光学吸收边蓝移,说明该材料 关键词： 多量子阱 量子限制效应 光学吸收 能带结构     

退火对Ge诱导晶化多晶Si薄膜结晶特性的影响

本文采用磁控溅射法, 衬底温度500 ℃下在硅衬底上分别制备具有Ge填埋层的a-Si/Ge 薄膜和a-Si薄膜, 并进行后续退火, 采用Raman光谱、X射线衍射、原子力显微镜及场发射扫描电镜等对所制薄膜样品进行结构表征. 结果表明, Ge有诱导非晶硅晶化的作用, 并得出以下重要结论: 衬底温度为500 ℃时生长的a-Si/Ge薄膜, 经600 ℃退火5 h Ge诱导非晶硅薄膜的晶化率为44%, 在相同的退火时间下退火温度提高到700 ℃, 晶化率达54%. 相同条件下, 无Ge填埋层的a-Si薄膜经800 ℃退火5 h薄膜实现晶化, 晶化率为46%. 通过Ge填埋层诱导晶化可使在相同的条件下生长的非晶硅晶薄膜的晶化温度降低约200 ℃. Ge诱导晶化多晶Si薄膜在Si(200)方向具有高度择优取向, 且在此方向对应的晶粒尺寸约为76 nm. 通过Ge诱导晶化制备多晶Si薄膜有望成为制备高质量多晶Si薄膜的一条有效途径.     

Structural and optical properties of Si/SiO2 multi-quantum wells

Structural and optical properties of Si/SiO₂ multi-quantum wells (MQW) were investigated by means of Raman scattering and photoluminescence (PL) spectroscopy. The MQW structures were fabricated on a quartz substrate by remote plasma enhanced chemical vapour deposition (RPECVD) of alternating amorphous Si and SiO₂ layers. After layer deposition the samples were subjected to heat treatments, i.e. rapid thermal annealing (RTA) and furnace annealing. Distinct PL signatures of confined carriers evidenced formation of Si-nanocrystals (nc-Si) in annealed samples. Analyses of Raman spectra also show presence of nc-Si phase along with amorphous-Si (a-Si) phase in the samples. The strong influence of the annealing parameters on the formation of nc-Si phase suggests broad possibilities in engineering MQW with various optical properties. Interestingly, conversion of the a-Si phase to the nc-Si phase saturates after certain time of furnace annealing. On the other hand, thinner Si layers showed a disproportionately lower crystalline volume fraction. From the obtained results we could assume that an interface strain prevents full crystallization of the Si layers and that the strain is larger for thinner Si layers. The anomalous dependence of nc-Si Raman scattering peak position on deposited layer thickness observed in our experiments also supports the above assumption.     

Polycrystalline silicon films prepared by metal-induced crystallisation using pre- and post-deposited aluminium on amorphous silicon

We report on the successful fabrication of polycrystalline silicon films by aluminium-induced crystallisation (AIC) of Radio frequency (rf) plasma-enhanced chemical vapour deposited (PECVD) a-Si films. The effects of annealing at different temperatures (300 and 400°C), below the eutectic temperature of the Si–Al binary system, on the crystallisation process have been studied. This work emphasises the important role of the position of the Al layer with respect to the Si layer on the crystallisation process. The properties of the crystallised films were characterised using X-ray diffraction, Raman spectroscopy, ellipsometry, field-emission scanning electron microscopy (FESEM) and atomic force microscopy (AFM). With an increase in the annealing temperature, it was found that the degree of crystallisation of annealed a-Si/Al and Al/a-Si films increased. The results showed that the arrangement where the Al was on top of the a-Si had a more prominent effect on crystallisation enhancement than when Al was below the a-Si. The interfacial layer between the Al and a-Si film is crucial because it influences the layer-exchange process during annealing. The oxide layer formed between the Al and the a-Si layers greatly retards the crystallisation process in the case of the Al/Si arrangement. Our investigations suggest that polycrystalline Si films formed by AIC can be used as a seed layer in solar cell fabrication.     

Characterizations of Tb:Zn2SiO4 films on silicon wafer prepared by sol-gel dip-coating and solid-phase reaction

Terbium-doped Zn_2SiO_4 films were successfully prepared on Si wafers by a simple sol-gel dip-coating and solid-phase reaction method of ZnO and SiO_2. X-ray diffraction (XRD) and UV－Vis absorption results revealed that films processed below 850℃ were ZnO in wurzite structure, and films processed above 850℃ were Zn_2SiO_4 in wellimite structure. Photoluminescence measurements of the Tb-doped Zn_2SiO_4 films showed two strong emission bands at 490 and 545nm. The photoluminescence lifetime was 4.6ms.     

Li_4SiO_4陶瓷小球水解吸行为实验研究

采用程序升温热解吸(TPD/TDS)方法对Li4SiO4陶瓷小球的水解吸行为进行了实验研究。结果表明:水解吸过程中主要存在四个解吸峰;其中100℃附近的峰可解释为物理吸附水;150,250,400℃附近的峰可分别解释为以氢键、Li-OH和Si-OH配位键形式存在的化学吸附水。氚的释放与水的解吸几乎同步进行,且氚的释放形式主要为氚水(HTO),据此推测,氚水可能存在三种释放机制:(1)-OT+H2O→-OH+HTO;(2)-OH+-OH→H2O,-OT+H2O→-OH+HTO;(3)-OT+-OH→HTO。     

The fabrication of nickel silicide ohmic contacts to n-type 6H-silicon carbide

This paper reports that the nickel silicide ohmic contacts to n-type 6H-SiC have been fabricated. Transfer length method test patterns with NiSi/SiC and NiSi硅化镍;欧姆触点;n型碳化硅;制造;能带;带隙Project supported by the National Basic Research Program of China (Grant No~2002CB311904), the National Defense Basic Research Program of China (Grant No~51327010101) and the National Natural Science Foundation of China (Grant No~60376001).2006-09-192006-10-30This paper reports that the nickel silicide ohmic contacts to n-type 6H-SiC have been fabricated. Transfer length method test patterns with NiSi/SiC and NiSi2/SiC structure axe formed on N-wells created by N^＋ ion implantation into Si-faced p-type 6H-SiC epilayer respectively. NiSi and NiSi2 films are prepared by annealing the Ni and Si films separately deposited. A two-step annealing technology is performed for decreasing of oxidation problems occurred during high temperature processes. The specific contact resistance Pc of NiSi contact to n-type 6H-SiC as low as 1.78× 10^-6Ωcm^2 is achieved after a two-step annealing at 350 ℃for 20 min and 950℃ for 3 min in N2. And 3.84×10-6Ωcm^2 for NiSi2 contact is achieved. The result for sheet resistance Rsh of the N＋ implanted layers is about 1210Ω/□. X-ray diffraction analysis shows the formation of nickel silicide phases at the metal/n-SiC interface after thermal annealing. The surfaces of the nickel silicide after thermal annealing are analysed by scanning electron microscope.     

Microstructure and lateral conductivity control of hydrogenated nanocrystalline silicon oxide and its application in a-Si:H/a-SiGe:H tandem solar cells

Phosphorous-doped hydrogenated nanocrystalline silicon oxide(n-nc-SiO_x:H) films are prepared via radio frequency plasma enhanced chemical vapor deposition(RF-PECVD). Increasing deposition power during n-nc-SiO_x:H film growth process can enhance the formation of nanocrystalline and obtain a uniform microstructure of n-nc-SiO_x:H film. In addition,in 20 s interval before increasing the deposition power, high density small grains are formed in amorphous SiO_x matrix with higher crystalline volume fraction(I_c) and have a lower lateral conductivity. This uniform microstructure indicates that the higher Ic can leads to better vertical conductivity, lower refractive index, wider optical band-gap. It improves the back reflection in a-Si:H/a-SiGe:H tandem solar cells acting as an n-nc-SiO_x:H back reflector prepared by the gradient power during deposition. Compared with the sample with SiO_x back reflector, with a constant power used in deposition process,the sample with gradient power SiO_x back reflector can enhance the total short-circuit current density(Jsc) and the initial efficiency of a-Si:H/a-SiGe:H tandem solar cells by 8.3% and 15.5%, respectively.     

Reaction between amorphous Si and crystalline Al in Al/Si and Si/Al bilayers: microstructural and thermodynamic analysis of layer exchange

Aluminium-induced crystallization of amorphous silicon (a-Si) in Al/Si and Si/Al bilayers was studied upon annealing at 250 °C by X-ray diffraction and Auger electron spectroscopy. The Al/a-Si bilayers and a-Si/Al bilayers were prepared by sputter deposition on single-crystal silicon wafers with a silicon-oxide film on top. During the isothermal annealing a layer-exchange process occurred in both types of bilayers. A continuous polycrystalline silicon (poly-Si) film was formed within, and thereby gradually replacing, the initial Al metal layer. The sublayer sequence in the original bilayer influenced the speed of the poly-Si formation and the layer-exchange process. After annealing, the Al fiber texture in the as-deposited bilayers had become stronger, the Al crystallites had grown laterally, and the macrostress in the Al layer had been released. The amorphous Si layer had crystallized into an aggregate of nanocrystals with {111} planes parallel to the surface, with a crystallite size of about 15–25 nm. An extensive analysis of the Gibbs energy change due to annealing showed that the layer exchange may be promoted by the release of elastic energy and grain growth for the Al phase. PACS 05.70.Jk; 61.43.Dq; 68.35.Rh; 61.72.Cc; 68.55.Jk     

Aluminium-induced crystallization of amorphous silicon films deposited by DC magnetron sputtering on glasses

Amorphous silicon (a-Si) and hydrogenated amorphous silicon (a-Si:H) films were deposited by DC magnetron sputtering technique with argon and hydrogen plasma mixture on Al deposited by thermal evaporation on glass substrates. The a-Si/Al and a-Si:H/Al thin films were annealed at different temperatures ranging from 250 to 550 °C during 4 h in vacuum-sealed bulb. The effects of annealing temperature on optical, structural and morphological properties of as-grown as well as the vacuum-annealed a-Si/Al and a-Si:H/Al thin films are presented in this contribution. The averaged transmittance of a-Si:H/Al film increases upon increasing the annealing temperature. XRD measurements clearly evidence that crystallization is initiated at 450 °C. The number and intensity of diffraction peaks appearing in the diffraction patterns are more important in a-Si:H/Al than that in a-Si/Al layers. Results show that a-Si:H films deposited on Al/glass crystallize above 450 °C and present better crystallization than the a-Si layers. The presence of hydrogen induces an improvement of structural properties of poly-Si prepared by aluminium-induced crystallization (AIC).     

Comparative study of spectroscopic properties of Er^3＋／Yb^3＋-codoped tellurite glass and fibres under 980nm excitation＊

A tellurite fibre of TeO_{2}－ZnO－La_{2}O_{3}－Li_{2}O glass codoped with 20000 ppm ytterbium and 5000 ppm erbium was fabricated by the suction casting and rod-in-tube technologies. The absorption spectrum of Er^{3+}/Yb^{3+} -codoped bulk glass has been measured. From the Judd－Ofelt intensity parameters, the spontaneous emission probability and radiative lifetime τ_{rad} of Er^{3+}:{}^{4}I_{13/2}→{}^{4}I_{15/2} transition for the bulk glass have been calculated. The emission fluorescence spectra and lifetimes around 1.5μm, and subsequent upconversion fluorescence in the range of 500－700nm were measured in fibres and compared with those in bulk glass. The changes in amplified spontaneous emission with fibre length and pumping power was also measured. It was found that the emission spectrum from erbium in fibres is almost twice as broad as the corresponding spectrum in bulk glass when pumped at 980nm.     

Studies of diamond-like carbon （DLC） films deposited on stainless steel substrate with Si/SiC intermediate layers

In this work, diamond-like carbon （DLC） films were deposited on stainless steel substrates with Si/SiC intermediate layers by combining plasma enhanced sputtering physical vapour deposition （PEUMS-PVD） and microwave electron cyclotron resonance plasma enhanced chemical vapour deposition （MW-ECRPECVD） techniques. The influence of substrate negative self-bias voltage and Si target power on the structure and nano-mechanical behaviour of the DLC films were investigated by Raman spectroscopy, nano-indentation, and the film structural morphology by atomic force microscopy （AFM）. With the increase of deposition bias voltage, the G band shifted to higher wave-number and the integrated intensity ratio ID/IG increased. We considered these as evidences for the development of graphitization in the films. As the substrate negative self-bias voltage increased, particle bombardment function was enhanced and the sp^3-bond carbon density reducing, resulted in the peak values of hardness （H） and elastic modulus （E）. Silicon addition promoted the formation of sp^3 bonding and reduced the hardness. The incorporated Si atoms substituted sp^2- bond carbon atoms in ring structures, which promoted the formation of sp^3-bond. The structural transition from C-C to C-Si bonds resulted in relaxation of the residual stress which led to the decrease of internal stress and hardness. The results of AFM indicated that the films was dense and homogeneous, the roughness of the films was decreased due to the increase of substrate negative self-bias voltage and the Si target power.     

nc-Si/SiO2多层膜的制备及蓝光发射

在等离子体增强化学气相淀积(PECVD)系统中，采用a-Si∶H层淀积与原位等离子体氧化相结合的逐层生长的方法成功制备出a-Si∶H/SiO2多层膜 (ML)；利用限制性结晶原理通过两步退火处理使a-Si∶H层晶化获得尺寸可控的nc-Si/SiO2 ML，并观察到室温下的蓝光发射；结合Raman散射和剖面透射电子显微镜技术分析了nc-Si/SiO2 ML的结构特性；通过对晶化样品光致发光谱和紫外-可见光吸收谱的研究，探讨了蓝光发射的起源. 关键词： 纳米硅多层膜 等离子体氧化 蓝光发射 热退火     

Magnetotransport properties and magnetocaloric effects of Mn1.95Cr0.05Sb0.95Ga0.05 compound

The magnetotransport properties and magnetocaloric effects of the compound Mn_{1.95}Cr_{0.05}Sb_{0.95}Ga_{0.05} have been studied. With decreasing temperature, a spontaneous first-order magnetic phase transition from ferrimagnetic (FI) to antiferromagnetic (AF) state takes place at T_s=200K. A metamagnetic transition from the AF to FI state can be induced by an external field, accompanied by a giant magnetoresistance effect of 57%. The magnetic entropy changes are determined from the temperature and field dependence of the magnetization using the thermodynamic Maxwell relation. Mn_{1.95}Cr_{0.05}Sb_{0.95}Ga_{0.05} exhibits a negative magnetocaloric effect, and the absolute values of ΔS_M^{max}(T,ΔH) are 4.4, 4.1, 3.6, 2.8 and 1.5 J/(kg·K) for magnetic field changes of 0－5T, 0－4T, 0－3T, 0－2T and 0－1T, respectively.     

Nuclear magnetic resonance investigation of H, H2 and dopants in hydrogenated amorphous silicon and related materials

Nuclear magnetic resonance has been successfully applied to the study of the microstructure of hydrogenated amorphous silicon and related materials. It has been used to determine the local bonding and structural environment of the host atoms, the hydrogen, and the dopants. First, we review some of these NMR experimental results on the hydrogen microstructure in hydrogentaed amorphous semiconductors and compare the results on plasma deposited hydrogenated amorphous silicon (a-Si:H), remote hydrogen plasma deposited a-Si:H, thermally annealed a-Si:H, doped a-Si:H, microcrystalline Si and amorphous (Si, Ge):H alloys. A common feature is that these materials exhibit a heterogeneous distribution of hydrogen bonded to the semiconductor lattice in dilute and clustered phases. In addition, the lattice contains voids of varying number and size that contain non-bonded molecular hydrogen whose quantity is altered by deposition conditions and thermal treatment. Second, we review some aspects of the local bonding structure of dopants in a-Si:H. A significant fraction of the dopants are found to be in dopant-hydrogen clusters similar to those proposed to explain hydrogen passivation in crystalline silicon. Implications of the determined local structure on the doping efficiency are discussed.