高压13.56MHz PECVD法沉积器件质量级本征微晶硅材料

本文国内首次报道了采用高压RF-PECVD技术沉积本征微晶硅材料的结果.实验表明,增大等离子体激发功率和减小硅烷浓度都能够使薄膜材料由非晶硅逐渐向微晶硅转变,而结构上的改变使得电学特性也随之改变.通过工艺参数的优化和纯化器的使用,有效地控制了氧的掺杂,在较高的生长速度下得到了器件质量级的本征微晶硅材料.将实验得到的微晶硅作为太阳电池光吸收层,在没有ZnO背电极和没有优化窗口层材料以及p/i界面时,电池的效率达到5.22;,这进一步表明本征微晶硅材料的良好性能.     

Advanced deposition phase diagrams for guiding Si:H-based multijunction solar cells

Phase diagrams have been established to describe very high frequency (vhf) plasma-enhanced chemical vapor deposition (PECVD) of intrinsic hydrogenated silicon (Si:H) and silicon–germanium alloy (Si_1?xGe_x:H) thin films on crystalline Si substrates that have been over-deposited with n-type amorphous Si:H (a-Si:H). The Si:H and Si_1?xGe_x:H films are prepared under conditions used for the top and middle i-layers of high efficiency triple-junction a-Si:H-based n–i–p solar cells. Identical n/i cell structures were co-deposited in this study on textured (stainless steel)/Ag/ZnO which serve as substrate/back-reflectors in order to relate the phase diagrams to the performance parameters of single-junction solar cells. This study has reaffirmed that the highest efficiencies for a-Si:H and a-Si_1?xGe_x:H solar cells are obtained when the i-layers are prepared under previously-described maximal H₂ dilution conditions.     

Light-induced changes in hydrogenated amorphous silicon solar cells deposited at the edge of crystallinity

A series of hydrogenated amorphous silicon (a-Si:H) films were deposited in the transition region from amorphous to nanocrystalline phases by changing hydrogen dilution ratio R, deposition gas pressure, and RF power. Single junction a-Si:H solar cells were made using these materials as the intrinsic layers in the structure of n–i–p type on ZnO/Ag/stainless steel substrates. Light-induced degradations in the photovoltaic parameters were characterized on these cells after 1 Sun solar illumination for 150 h. The stabilized efficiencies were compared in conjunction with the structures in the intrinsic layers, which were revealed by high resolution transmission electron microscopy (HRTEM) and Fourier transform infrared spectrometry (FTIR). It was found that the solar cells incorporated protocrystalline intrinsic layer as the i-layer give a better initial efficiency, while solar cells made from nanostructured i-layers have a better stability of ～7% degradation against light soaking, as a result, both have nearly the same final stabilized efficiency. The best device stabilized efficiency reaches ～10.2% (0.25 cm², AM1.5G) for the intrinsic layer deposited at a high pressure of 2 Torr.     

Enhanced spectral response by silicon nitride index matching layer in amorphous silicon thin-film solar cells

We employed the low temperature hydrogenated amorphous silicon nitride (a-SiN_x:H) prepared by plasma-enhanced chemical vapor deposition as a refractive index (n) matching layers in a silicon-based thin-film solar cell between glass (n = 1.5) and the transparent conducting oxide (n = 2). By varying the stoichiometry, refractive index and thickness of the a-SiN_x:H layers, we enhanced the spectral response and efficiency of the hydrogenated amorphous silicon thin-film solar cells. The refractive index of a-SiN_x:H was reduced from 2.32 to 1.78. Optimizing the a-SiN_x:H thickness to 80 nm increased the J_SC from 8.3 to 9.8 mA/cm² and the corresponding cell efficiency increased from 4.5 to 5.3%, as compared to the cell without the a-SiN_x:H index-matching layer on planar substrate. The a-SiN_x:H layers with graded refractive indices were effective for enhancing the cell performance.     

Characterization of hydrogenated amorphous silicon thin films prepared by magnetron sputtering

Magnetron sputtered hydrogenated amorphous silicon (a-Si:H) thin films have been characterized. Hydrogen (H₂) with argon (Ar) was introduced into the sputtering chamber to create the plasma. A sudden increase in the deposition rate occurred when the hydrogen was added. The maximum hydrogen content of 16 atomic percent (at.%) was achieved and a bandgap of about 2.07 eV was determined from the spectral investigations of the hydrogenated films. The effect of radio frequency (RF) power on the deposition rate, as well as on the hydrogen content was investigated. To change the hydrogen content in the films, the hydrogen flow rate was varied while keeping the argon flow rate constant. The hydrogen content in the films increased with increasing hydrogen flow rate up to the maximum content of 16 at.% and then decreased for further increases in hydrogen flow.     

Optimization and characterization of i/p buffer layer in hydrogenated nanocrystalline silicon solar cells

The effect of a-Si:H i/p buffer layer on the performance of nc-Si:H solar cells is studied systematically. The results show that for thin nc-Si:H cells, an optimized i/p buffer layer significantly reduces the dark current thus increases the open-circuit voltage. We believe that the carrier recombination at the i/p interface is one of the determining factors for the nc-Si:H cell performance, especially for cells with a thin intrinsic layer. Therefore, optimizing the i/p buffer layer is one of the key factors for achieving high efficiency nc-Si:H solar cells. This interface effect is less pronounced as the nc-Si:H intrinsic layer thickness increases, where the recombination in the bulk becomes a dominant factor. Combining the improved nc-Si:H intrinsic layer with a proper hydrogen dilution and an optimized a-Si:H i/p buffer layer, the performance of nc-Si:H single-junction and a-Si:H/a-SiGe:H/nc-Si:H triple-junction cells is significantly improved.     

Interface properties of amorphous-crystalline silicon heterojunctions prepared using DC saddle-field PECVD

The planar conductance technique has been previously used in the study of amorphous silicon/crystalline silicon (a-Si:H/c-Si) heterojunctions, grown using conventional Radio Frequency Plasma Enhanced Chemical Vapor Deposition (RF-PECVD), to examine the existence of a strong inversion layer at the c-Si surface. In the present study such measurements were undertaken on a series of heterojunctions in order to provide insight into the nature of the electrical interface between the hydrogenated amorphous silicon, deposited using the DC Saddle Field PECVD system, and the underlying crystalline silicon wafer. The films showed good passivation and a strong inversion layer, indicating their amenability for device applications.     

Transport properties and defects in silicon nanoparticles and effect of embedding in amorphous silicon layers

We study the properties of silicon nanoparticles produced by CO₂ laser pyrolysis of silane in a gas flow reactor, and the effect of sandwiching a thin layer of such particles between two a-Si:H layers. Contrary to the case of hydrogenated polymorphous silicon for which it is known that the electronic and stability properties can be enhanced compared to conventional hydrogenated amorphous silicon, the electronic properties of such a sandwich structure are degraded and the number of deep defects is increased.     

数值模拟p/i界面对微晶硅薄膜太阳电池性能的影响

采用美国宾州大学开发的AMPS(Analysis of Microelectronic and Photonic Structures)软件模拟了p/i界面缺陷态密度(Npt/i)和非晶孵化层厚度(d)对pin型氢化微晶硅(μc-Si:H)薄膜太阳电池性能的影响.结果表明:随着Npt/i的增大,电池的开路电压Voc和填充因子FF单调减小,短路电流Jsc基本不变;随着d的增大,Jsc和FF单调减小,Voc反而增大;Npt/i和d值的增大均会导致电池光电转换效率η下降.通过对电池内部的电场及能带的分析,对上述模拟结果进行了解释.     

Hydrogenated microcrystalline silicon thin films deposited by RF-PECVD under low ion bombardment energy using voltage waveform tailoring

We present experimental results for hydrogenated amorphous and microcrystalline silicon (a-Si:H and μc-Si:H) thin films deposited by PECVD while using a voltage waveform tailoring (VWT) technique to create an electrical asymmetry in the reactor. VWT dramatically modifies the mean ion bombardment energy (IBE) during growth, and we show that for a constant peak-to-peak excitation voltage (V_PP), waveforms resembling “peaks” or “valleys” result in very different material properties. Using Raman scattering spectroscopy, we show that the crystallinity of the material depends strongly on the IBE, as controlled by VWT. A detailed examination of the Raman scattering spectra reveals that the narrow peak at 520 cm^? 1 is disproportionately enhanced by lowering the IBE through the VWT technique. We examine this effect for a range of process parameters, varying the pressure, hydrogen–silane dilution ratio, and total flow of H₂. In addition, the SiH_X bonding in silicon thin films deposited using VWT is characterised for the first time, showing that the hydrogen bonding character is changed by the IBE. These results demonstrate the potential for VWT in controlling the IBE during thin film growth, thus ensuring that application-appropriate film densities and crystallinities are achieved, independent of the injected RF power.     

Influence of hydrogen on structural and optical properties of low temperature polycrystalline Ge films deposited by RF magnetron sputtering

To improve the properties of polycrystalline Ge thin films, which are a candidate material for the bottom cells of low cost monolithic tandem solar cells, ∼300 nm in situ hydrogenated Ge (Ge:H) thin films were deposited on silicon nitride coated glass by radio-frequency magnetron sputtering. The films were sputtered in a mixture of 15 sccm argon and 10 sccm hydrogen at a variety of low substrate temperatures (T_s)≤450 °C. Structural and optical properties of the Ge:H thin films were measured and compared to those of non-hydrogenated Ge thin films deduced in our previous work. Raman and X-ray diffraction spectra revealed a structural evolution from amorphous to crystalline phase with increase in T_s. It is found that the introduction of hydrogen gas benefits the structural properties of the polycrystalline Ge film, sputtered at 450 °C, although the onset crystallization temperature is ∼90 °C higher than in those sputtered without hydrogen. Compared with non-hydrogenated Ge thin films, hydrogen incorporated in the films leads to broadened band gaps of the films sputtered at different T_s.     

沉积温度对等离子体化学气相沉积制备硅氧薄膜微结构的影响

利用13.56 MHz的射频等离子体化学气相沉积设备(RF-PECVD)在不同沉积温度(50~400 ℃)下制备了一系列氢化硅氧(SiO_x:H)薄膜材料,并研究了薄膜材料性能与微结构的变化规律。随着沉积温度的增加,薄膜内的氧含量(C_O)下降,晶化率(X_C)也下降,折射率(n)上升,此外,薄膜的结构因子(R)下降,氢含量(C_H)先上升后下降,由此在合适的中间温度下可以获得最大的氢含量。通过实验结果分析提出了不同沉积温度下制备硅氧薄膜的内在微结构模型:低温下沉积的硅氧薄膜是以氢化非晶硅氧(a-SiO_x:H)相为主体并嵌入氢化纳米晶硅(nc-Si:H)的复合材料,而在高温下沉积的硅氧薄膜则是以氢化非晶硅(a-Si:H)相为主体并嵌入越来越少的nc-Si:H相和a-SiO_x:H相的复合材料。由上可知,要制备太阳电池通常采用的晶化率X_C高、氧含量C_O高的氢化纳米晶硅氧(nc-SiO_x:H)材料,需要采用相对较低的沉积温度。     

Microcrystalline silicon oxide (μc-SiOx:H) alloys: A versatile material for application in thin film silicon single and tandem junction solar cells

We report on the development and application of n-type hydrogenated microcrystalline silicon oxide (μc-SiO_x:H) alloys in single and tandem junction thin film silicon solar cells. Single junction microcrystalline silicon (μc-Si:H) solar cells are prepared in n-i-p deposition sequence where n-type μc-SiO_x:H films serve as window layers. In tandem solar cells, μc-SiO_x:H layers are placed between amorphous (a-Si:H) and μc-Si:H component cells, serving as an intermediate reflector. The requirements for μc-SiO_x:H layer depending on its application are discussed. Our results show that the optical, electrical and structural properties of μc-SiO_x:H can be conveniently tuned over a wide range to fulfil various requirements for applications in both types of cells. Additionally, the properties of μc-SiO_x:H layers appear to be substrate dependent, which should be taken into account when layers are utilized in cells. The advantages of low refractive index and high optical band gap allow to achieve high efficiencies of 9.2% and 12.6% for single junction and tandem solar cells, respectively.     

Two-dimensional modelling and simulation of hydrogenated amorphous silicon p-n-n solar cell

Two-dimensional device modelling for hydrogenated amorphous silicon p⁺-n-n⁺ solar cell has been carried out by using MEDICI^™ device simulator and the influence of absorber layer thickness, doping concentration, and dangling bond density of states in absorber layer on photo parameters are investigated. A strong correlation between n-type doping and dangling bond density in the absorber layer relative to the stability of the a-Si:H solar cell is observed. An increased stabilized efficiency is obtained when n-type dopant concentration in the absorber layer is higher than optimum value for higher initial efficiency. The window layer (p⁺ layer) of the device is designed with a three layered structure of graded doping for higher device performance. This window layer structure in the a-Si:H p⁺-n-n⁺ cell resulted in higher open circuit voltage and fill factor and hence higher efficiency of the cell. The efficiency of the modified amorphous silicon solar cell structure is found to be 12.85%.     

The characteristics of solid phase crystallized (SPC) polycrystalline silicon thin film transistors employing amorphous silicon process

We investigated the electrical properties of polycrystalline silicon (poly-Si) thin film transistors (TFTs) employing field-enhanced solid phase crystallization (FESPC). An n+ amorphous silicon (n+ a-Si) layer was deposited to improve the contact resistance between the active Si and source/drain (S/D) metal instead of ion doping. By using C–V measurement method, we could explain the diffused phosphorous ions (P+ ions) on the channel surface caused a negatively shifted threshold voltage (V_TH) of ?7.81 V at a drain bias of 0.1 V, and stretched out a subthreshold swing (S) of 1.698 V/dec. This process was almost compatible with the widely used hydrogenated amorphous silicon (a-Si:H) TFT fabrication process and also offers a better uniformity when compared to the conventional laser-crystallized poly-Si TFT process because of non-laser crystallization.     

Device grade hydrogenated polymorphous silicon deposited at high rates

Hydrogenated polymorphous silicon (pm-Si:H) thin films have been deposited by plasma-enhanced chemical vapor deposition at high rate (8–10 Å/s), and a set of complementary techniques have been used to study transport, localized state distribution, and optical properties of these films, as well as the stability of these properties during light-soaking. We demonstrate that these high deposition rate pm-Si:H films have outstanding electronic properties, with, for example, ambipolar diffusion length (L_d) values up to 290 nm, and density of states at the Fermi level well below 10¹⁵ cm^?3 eV^?1. Consistent with these material studies, results on pm-Si:H PIN modules show no dependence of their initial efficiency on the increase of the deposition rate from 1 to 10 Å/s. Although there is some degradation after light-soaking, the electronic quality of the films is better than for degraded standard hydrogenated amorphous silicon (values of L_d up to 200 nm). This result is reflected in the light-soaked device characteristics.     

Carrier collection characteristics of microcrystalline silicon–germanium p–i–n junction solar cells

We report on the carrier collection characteristics of hydrogenated microcrystalline silicon–germanium (μc-Si_1?xGe_x:H) p–i–n junction solar cells fabricated by low-temperature (～200 °C) plasma-enhanced chemical vapor deposition. Spectral response measurements reveal that the Ge incorporation into absorber i-layer reduces the quantum efficiencies at short wavelengths. Furthermore, the illumination of the solar cells for x ? 0.35, particularly in the wavelength range of <650 nm, induces a strong injection-level-dependent p–i interface recombination and a weak collection enhancement in the bulk. These results indicate that space charges near the p–i interface are largely negative, which gives rise to an electric field distortion in the i-layer. We attribute the negative space charges to the presence of the acceptor-like states that are responsible for the strong p-type conduction observed in undoped μc-Si_1?xGe_x:H films for large Ge contents.     

Lateral photovoltage measurements in hydrogenated amorphous silicon and silicon-oxygen thin films

Hydrogenated amorphous silicon (a-Si:H) and hydrogenated amorphous silicon-oxide alloy films (a-SiO_x:H) were investigated by temperature dependence of lateral photovoltage (LPV) measurements. The suboxide sample with [O] = 27 at.%, was found to exhibit larger LPV compared to the unalloyed sample. It is difficult to simply correlate LPV measurements to related diffusion length measurements, only. On the other hand, the observed magnitude of LPV in a-Si:H and its decrease with temperature, could be explained based on an internal electric field induced by diffusion electron and hole currents, and multiple trapping of the photocarriers.     

Influence of the amorphous/crystalline silicon heterostructure properties on planar conductance measurements

We report a quasi-analytical calculation describing the heterojunction between hydrogenated amorphous silicon (a-Si:H) and crystalline silicon (c-Si) at equilibrium. It has been developed and used to determine the carrier sheet density in the strongly inverted layer at the a-Si:H/ c-Si interface. The model assumes an exponential band tail for the defect distribution in a-Si:H. The effects of the different parameters involved in the calculation are investigated in detail, such as the Fermi level position in a-Si:H, the density of states and the band offsets. The calculation was used to interpret temperature dependent planar conductance measurements carried out on (n) a-Si:H/ (p) c-Si and (p) a-Si:H/(n) c-Si structures, which allowed us to confirm a previous evaluation of the conduction band offset, ?E_C = 0.18 ± 0.05 eV, and to evaluate the valence band offset: ?E_V = 0.36 ± 0.05 eV at the a-Si:H/ c-Si heterojunction. The results are placed in the frame of recent publications.     

Optical and electrical properties of chlorinated and hydrogenated amorphous silicon prepared by glow discharge

Chlorinated and hydrogenated amorphous silicon films were prepared by glow discharge of a SiCl₄/H₂ mixture. Infrared spectra of these films show that, in addition to the hydrogen induced bands, two new modes appear at 545 cm^?1 (SiCl stretching) and 500 cm^?1 (Si TO modes induced by chlorine). Observation of the 545 cm^?1 band proves that chlorine is able to act as a dangling bond terminator in an amorphous silicon matrix. A good agreement is found between the total amount of chlorine determined by electron microprobe analysis and the value estimated from the integrated strength of the SiCl stretching mode. The relatively high value of the optical band gap (1.80 eV) of our material containing only 5 at.% bonded hydrogen shows that chlorine plays a major role in the optical gap value. Electrical conductivity, photoconductivity and luminescence properties are qualitatively similar to that of a: SiH films.