Amorphous thin-film solar cells

This report gives an overview of the present status of thin-film solar cells made from hydrogenated amorphous semiconductors (a-Si:H, a-Ge:H) together with new results emphasizing the physics of amorphous materials and devices. Preparation techniques, quality and performances of a-Si:H and a-Ge:H films as well as solar cells with pin structures are reviewed. Dark and light current-voltage I(V) characteristics and spectral response measurements give information about photovoltaic diodes and allow further insights into the physics of these kinds of materials and solar cells. Simulation calculations and device modelling of such solar cells have increased our understanding of amorphous semiconductors and their devices. The introduction of pin/pin stacked and/or tandem structures has improved the long-term stability and conversion efficiency of amorphous solar cells.Dedicated to H.-J. Queisser on the occasion of his 60th birthday     

a-Si:H/a-SiNx:H超晶格薄膜光致发光性质的研究

本文报道了a-Si:H/a-SiNx:H超晶格薄膜光致发光某些性质的研究。实验发现,这种超晶格薄膜光致发光的强度和峰值能量随交替层a-Si:H厚度,测量温度及光照时间等而变化。同时还发现,在阴、阳两极上,利用GD法沉积的样品,发光强度和峰值能量也有所不同。文中对这些实验结果作了初步解释。     

Understanding of a-Si:H(p)/c-Si(n) heterojunction solar cell through analysis of cells with point-contacted p/n junction

We fabricated point-contacted a-Si:H(p)/c-Si(n) heterojunction solar cells using patterned SiO₂ and investigated their electrical properties using the light current–voltage (I–V) curve and Suns-V_oc measurements. The light I–V curves showed bias-dependent changes according to the applied voltage in the point-contacted cells, especially in the samples with a long distance between the point-contacted junctions. The Suns-V_oc measurements showed that the bias-dependence of the light I–V curves did not originate from the recombination in the SiO₂/Si or a-Si:H(p)/c-Si(n) interface, but from the series resistances. It is possible to explain the bias-dependent light I–V curve in terms of the conductivity of a-Si:H(p) and difference in the electrical contact properties between a-Si:H(p), ZnO and c-Si(n). These results mean that the electrical properties of the a-Si:H(p) layer and the contact properties with this layer are also critical to obtain a high J_sc and fill factor in n-type based Si heterojunction solar cells.     

椭偏透射法测量氢化非晶硅薄膜厚度和光学参数

针对多角度椭偏测量透明基片上薄膜厚度和光学参数时基片背面非相干反射光的影响问题,报道了利用椭偏透射谱测量等离子增强化学气相沉积法(PECVD)制备的a-Si:H薄膜厚度和光学参数的方法,分析了基片温度T_s和辉光放电前气体温度T_g的影响.研究表明,用椭偏透射法测量的a-Si:H薄膜厚度值与扫描电镜(SEM)测得的值相当,推导得到的光学参数与其他研究者得到的结果一致.该方法可用于生长在透明基片上的其他非晶或多晶薄膜. 关键词： 椭偏测量 透射法 光学参数 氢化非晶硅薄膜     

A thin-film transistor with a very thin a-Si:H layer and its application for an LC panel

One of the disadvantages of applying an a-Si:H thin-film transistor (TFT) to an active matrix-addressed liquid crystal (LC) panel is that a TFT with an a-Si:H has a very large photo-leakage current because of the high photo-conductivity of an a-Si:H itself.We have tried decreasing the photo-leakage current by varying the thickness of an a-Si:H layer (L) in TFTs and investigated the characteristics of TFTs, mainly drain voltage versus drain current containing photo-leakage current (I _ph).As a result, it is shown that lnI _ph is proportional to InL, and its gradient is 1.5–2.0. We assume that the thinner an a-Si:H layer is, the more effective the recombination of carriers at the interface states is forI _ph.We have applied TFT with a very thin a-Si:H layer (30nm) to a full-color active matrix-addressed LC panel for a moving picture display and realized a display of good quality under illuminated condition of 5×10⁴lx without a shading layer in it.     

B掺杂a-SiC:H/本征a-Si:H异质结中的B扩散

本文用 ¹¹B(p,a)⁸ Be(E_{r=163keV)核反应分析方法,研究不同生长温度和退火温度对a-SiC:H(B)/a-Si:H异质结构中B原子浓度剖面分布的影响,由B原子浓度剖面分布的变化,分别估算了B在a-Si:H生长和退火过程中的扩散系数,结合电导率随膜厚度变化的测量,并依据最新提出的热平衡缺陷观点,对B的扩散过程作了分析。 关键词：}     

Influence of heterogeneities on the electronic properties of hydrogenated amorphous silicon

An attempt is made to highlight the importance of inhomogeneities in hydrogenated amorphous silicon (a-Si:H), in controlling its electronic properties. We note that hydrogen increases the gap in a-Si:H and that hydrogen is distributed inhomogeneously in it. This gives rise to long-range potential fluctuations, which are mostly uncorrelated and usually ignored. These and other such considerations have not only enabled us to gain new insights into the behaviour of a-Si:H in general, but have also allowed us to resolve several unsolved puzzles. Among these are questions like why undoped a-Si:H is n-type, why the creation of dangling bonds upon light soaking (LS) so inefficient, why a-Si:H degrades more upon LS when it is doped, why the reciprocity fails for light-induced degradation, why presence of nanocrystalline silicon improves stability and so on. We provide evidence to support some of our ideas and make suggestions for verifying the others.     

Hydrogen evolution during deposition of microcrystalline silicon by chemical transport

We exposed a freshly deposited boron-doped, hydrogenated amorphous silicon (a-Si:H) layer to hydrogen plasma under conditions of chemical transport. In situ spectroscopic ellipsometry measurements revealed that atomic hydrogen impinging on the film surface behaves differently before and after crystallization. First, the plasma exposure increases hydrogen solubility in the a-Si:H network leading to the formation of a hydrogen-rich subsurface layer. Then, once the crystallization process engages, the excess hydrogen starts to leave the sample. We have attributed this unusual evolution of the excess hydrogen to the grown hydrogenated microcrystalline (μc-Si:H) layer, which gradually prevents the atomic hydrogen from the plasma reaching the μc-Si:H/a-Si:H interface. Consequently, hydrogen solubility, initially increased by the hydrogen plasma, recovers the initial value of an untreated a-Si:H material. To support the theory that the outdiffusion is a consequence and not the cause of the μc-Si:H layer growth, we solved the combined diffusion and trapping equations, which govern hydrogen diffusion into the sample, using appropriate approximations and a specific boundary condition explaining the lack of hydrogen injection during μc-Si:H layer growth.     

Electroforming of thin film silicon based homojunction pin diode

The recent observations of bright visible electroluminescence (EL) from electroformed thin film silicon based wide-gap alloys are further clamped down in a simpler structure. For this purpose, a standard quality, ordinary hydrogenated amorphous silicon (a-Si:H) homojunction pin diode was fabricated by plasma enhanced chemical vapor deposition. The fresh diode was characterized by temperature scanned current–voltage (I–V) and constant photocurrent measurements. The energy distribution of density of states within the forbidden gap of the intrinsic a-Si:H layer was determined by space charge limited current and optical absorption spectroscopies. Then the diode was intentionally subjected to a sufficiently high, calibrated electric field leading to its Joule heating assisted rapid crystallization at ambient atmosphere. The fresh and the formed diodes exhibit different I–V and EL characteristics. The current density of the formed diode increases drastically at low voltages while remaining unchanged at high voltages when compared to that of the fresh diode. Parallelly, the room temperature EL intensity under a particular current stress is boosted with electroforming. These interesting phenomena have been discussed in the frame of a self-consistent model.     

Thermal annealing of a-Si:H/a-SiNx:H multilayers

The crystallinity of Si/SiN_x multilayers annealed by a rapid thermal process and furnace annealing is investigated by a Raman-scattering technique and transmission electron microscopy. It is found that the crystallization temperature varies from 900 °C to 1000 °C when the thickness of a-Si:H decreases from 4.0 nm to 2.0 nm. Raman measurements imply that the high crystallization temperature for the a-Si:H sublayers originates from the confinement modulated by the interfaces between a-Si:H and a-SiN_x:H. In addition to the annealing temperature, the thermal process also plays an important role in crystallization of a-Si sublayers. The a-Si:H sublayers thinner than 4.0 nm can not be crystallized by furnace annealing for 30 min, even when the annealing temperature is as high as 1000 °C. In contrast, rapid thermal annealing is advantageous for nucleation and crystallization. The origin of process-dependent crystallization in constrained a-Si:H is briefly discussed. Received: 11 April 2001 / Accepted: 20 June 2001 / Published online: 30 August 2001     

Determination of electron-diffusion length from photocurrent characteristics of the structure ITO/a-SiC:H(p-type)/a-Si:H/a-Si:H(n-type)/Pd

In this study the electron diffusion length L _n is determined from the relative spectral response of the photocurrent characteristics of the p/i/n sandwich structure ITO/a-SiC:H(p-type)/a-Si:H/a-Si:H(n-type)/Pd. The techniques used for the preparation of the a-Sic:H and a-Si:H amorphous films were glow-discharge and rf magnetron sputtering, respectively. The thickness of the p-type, intrinsic and n-type layer were 400 Å, 7000 Å and 600 Å, respectively. The response of the short-circuit current density J _sc was measured versus the photon energy hv at both constant light intensity and constant temperature. The electron diffusion length was found to be 0.31 m by means of the method of Agarwala and Tewary. Although, in the case of single crystals many diffusion length measurements have been made, there are only few papers for amorphous silicon this films [1]. As it is well-known, the diffusion length of the charge carriers is the most important parameter from the point of view of solar cell applications [2]. In order to obtain a high efficiency in a solar cell all carriers created under illumination in the intrinsic layer should reach the electrodes [3]. In the case that the thickness of the intrinsic layer is much larger than the diffusion length, not all carriers can reach the electrodes and, accordingly, a low efficiency results [4]. On the other hand, carriers which reach the electrodes without thermalizing do not contribute to the photocurrent and finally the efficiency of the solar cell is negatively affected. In order to avoid such an effect to a large extent, the thickness of the amorphous layers in a p/i/n solar cell must be conveniently chosen compared to the diffusion length of the carriers.Here it is aimed to determine the electron diffusion length. In order to achieve this goal, the photocurrent characteristics of an ITO/a-SiC:H(p-type)/a-Si:H/a-Si:H(n-type)/Pd structure was measured versus the photon energy at constant light intensity and constant temperature. In order to determine the electron diffusion length, the method of Agarwala and Tewary [5] was utilized.     

The p recombination layer in tunnel junctions for micromorph tandem solar cells

A new tunnel recombination junction is fabricated for n–i–p type micromorph tandem solar cells. We insert a thin heavily doped hydrogenated amorphous silicon (a-Si:H) p + recombination layer between the n a-Si:H and the p hydrogenated nanocrystalline silicon (nc-Si:H) layers to improve the performance of the n–i–p tandem solar cells. The effects of the boron doping gas ratio and the deposition time of the p-a-Si:H recombination layer on the tunnel recombination junctions have been investigated. The current-voltage characteristic of the tunnel recombination junction shows a nearly ohmic characteristic, and the resistance of the tunnel recombination junction can be as low as 1.5 ·cm 2 by using the optimized p-a-Si:H recombination layer. We obtain tandem solar cells with open circuit voltage V oc = 1.4 V, which is nearly the sum of the V oc s of the two corresponding single cells, indicating no V oc losses at the tunnel recombination junction.     

Electrical properties and degradation behavior of hydrogenated amorphous Si alloys for solar cells

The electrical properties and the degradation behavior of hydrogenated amorphous silicon alloys (a-Si_1–x A _x : H, with A=C, Ge, B, P) in designs of pin, pip, nin, and MOS structures are investigated by measuring the dark and light I(V) characteristics and the spectral response as well as the space-charge-limited current (SCLC), the time of flight (TOF) of carriers and the field effect (FE). These investigations give an overview of our recent work combined with new results emphasizing the physics of the a-Si:H pin solar cells. We discuss the stabilizing influence on the degradation behavior achieved by profiling the i layers of the pin solar cells with P and B. Two kinds of pin solar cells, namely glass/SnO₂/p(C)in/metal and glass/metal/pin/ITO, are investigated and an explanation of their different spectral response behavior is given. SCLC measurements lead to the conclusion that trapping is also involved in the degradation mechanism, as is recombination. TOF experiments on a-Si_1–x Ge _x : H pin diodes indicate that the incorporation of Ge widens the tail-state distribution below the conduction band. FE measurements showed densities of gap states of about 5×l0¹⁶cm^–3eV^–1.     

Preparation and properties of Er and Yb doped InP-based semiconductor compounds

In this paper we pursue the effect of the erbium and ytterium addition during the liquid phase epitaxial (LPE) growth on physical properties of thin InP layers. Series of InP layer samples were prepared by LPE from the melts containing 0–0.3 wt.% of Er and Yb. The grown layers were examined by the Hall effect andC-V measurements, photoluminescence spectroscopy and Rutherford backscattering spectrometry (RBS). We have found that only Yb impurity was incorporated into the lattice of InP layer. With increasing Yb content in the growth melt the layer’s conductivity smoothly changed from n to p type when Yb admixture exceeded certain limit. On the basis of these results we prepared p-n junctions in the InP layers directly doped by Yb, and tested then byC-V measurements. Presented at the 1st Czech-Chinese Workshop “Advanced Materials for Optoelectronics”, Prague, Czech Republic, June 13–17, 1998. This work has been supported by the Grant Agency of the Czech Republic, project No. 102/99/0341.     

Microwave impedance measurements on resonant tunnelin diodes with asymmetric spacer layers

Scattering parameters (S parameters) have been measured up to 40GHz on GaAs/AlAs resonant tunneling diodes containing asymmetric spacer layers. On-wafer microwave probing techniques were used. A hysteresis was observed in the vicinity of the negative differential resistance (NDR) region. Unlike the one observed in dc current-voltage measurements, this hysteresis was not affected by oscillations and believed to be intrinsic. The impedance data has been fitted to a lumped equivalent circuit model and capacitance-voltage (C-V) characteristic extracted. In addition to the already reported capacitance peak in the NDR region, a smaller peak at a lower voltage was found. In comparison to the self-consistent calculation, the smaller peak is due to the electrons discharging from accumulation region between the emitter barrier and the cathode spacer layer. The C-V result agrees qualitatively with the theoretical calculation. It supports the theoretical argument that the negative conductance can be increased by increasing the cathode spacer layer, however, there is also an increase in capacitance and the cutoff frequency may be reduced.     

Angular distribution of intensity of reflected radiation investigations of the influence of CO2 laser treatment on optical properties of hydrogenated amorphous silicon

Thin films of hydrogenated amorphous silicon (a-Si:H) were annealed using CO₂ laser radiation (λ=10.6 μm). Changes of optical properties of the treated a-Si:H were investigated using optical transmittance spectroscopy and the angular distribution of intensity of reflected radiation (ADIRR). The CO₂ laser annealing influences the spectral characteristics of the real part of refractive index n and absorption coefficient α of light in a-Si:H. This treatment increases the n and α values as well as the Urbach energy of a-Si:H. Simultaneously it decreases the optical energy gap of this material. The changes of optical parameters at the interfaces of a-Si:H–glass substrate and a-Si:H–air were established.     

非晶半导体光致发光的温度依赖关系

研究了a-Si:H,a-Si:H,F,a-Si:H,Cl以及a-Si:H,Cl,O等非晶硅薄膜光致发光的温度依赖关系。测量了各种样品的无辐射跃迁激活能ε,并试图寻求激活能ε与样品的制备条件和结构之间的关系;同时从发光强度的温度相关性确定了带尾态密度分布参数T0,以及T0与发光光谱形状之间的关系。并将实验结果与瞬态光电导的数据进行了比较。     

生长过程中磷压对MOVPE GaP电致发光谱的影响

对在不同磷压下生长的MOVPE GaP二极管的电致发光(EL)谱进行了测量。参照对相应的肖特基势垒样品进行的结技术测量和对衬底进行的光致发光(PL)测量结果,对观测到的几个强度随生长时所用磷压明显变化的EL带的起因作了讨论。将其中相对强度随磷压增加的两个EL带分别试归因于与反位磷PGa的一次和二次离化态有关的辐甜复合;将相对强度随磷压减小而增大的一个EL带归因于与氧有关。     

Theoretical analysis on the limitations of the open-circuit voltage of a hydrogenated amorphous silicon p-i-n solar cell

We have made theoretical studies on the limitation of the open-circuit voltageV _oc of a hydrogenated amorphous silicon (a-Si:H) p-i-n type solar cell. The effects of the tail states in the a-Si:H i layer and of the interface recombination are discussed in detail. The opencircuit voltage increases when the distribution of the tail states is sharp and/or the capture cross sections of these states are small. This is because the recombination rate of photogenerated carriers and/or the density of space charge due to trapped carriers in these states become low in these conditions. These effects of the tail states on the value ofV _oc become pronounced when the built-in potential of the p-i-n junction is high. The decrease in the effective recombination velocity of carriers at the p/i and n/i interfaces results in an increase ofV _oc. This increase becomes remarkable when the effects of the tail states on the value ofV _oc are small. Both the sharp distribution of tail states and the small value of the interface recombination velocity are necessary to increase considerably the value ofV _oc. We show the conditions of the material parameters necessary to obtain an open-circuit voltage of 1.0 V.     

Effects of gas temperature on optical and transport properties of a-Si:H films deposited by PECVD

Effects of silane temperature (T _g) before glow-discharge on the optical and transport properties of hydrogenated amorphous silicon (a-Si:H) thin films were investigated. The optical measurements show that the refractive index increases with increasing T _g. The transport characterizations show that when T _g increases, the dark conductivity increases. However, the temperature coefficient of resistance decreases. In addition, after holding at 130°C for 20 h, the resistance variation, ΔR/R, of the films deposited at T _g = room temperature (10.8%) is much larger than those deposited at silane temperatures of 80°C (3%) and 160°C (2%). This can be attributed to different rates of defect creation in a-Si:H films caused by various T _g.