Arresting photodegradation of porous silicon by a polymer coating

Light soaking in air rapidly decreases photoluminescence (PL) of porous silicon (PS) and increases electron spin resonance (ESR) signal. In vacuum, a short light exposure (<2700 s) increases PL and decreases ESR, but longer exposures again degrade the PL. We could arrest the light-induced degradation over long periods by applying a thin polymer coating, which resulted in constant PL and ESR intensities. The PL intensity of coated PS is comparable to the PL intensity of a fresh PS sample in air. FTIR spectrum suggests new bond formations at the PS/polymer interface that may be responsible for PL stability.     

Quantum confinement and disorder in porous silicon: Effects on the optical and transport properties

Summary The striking optical properties of porous silicon (PS) show a twofold aspect typical of an ordered and a disordered material, respectively. Raman, electron microscopy, and resonant photoluminescence studies indicate that the light emission originates from crystalline regions. On the contrary, several features, like the non-exponential decay of photoluminescence (PL), the broad emission spectrum, the photoluminescence fatigue under light exposure etc. are typical of a disordered material and reminiscent of similar effects founde.g. in amorphous semiconductors. These twoapparently conflicting aspects have for a long time hindered the understanding of the basic light emission mechanism. In this paper we report new optical data showing that disorder in porous silicon leads to strong carrier localisation. Light emission in PS is suggested to occur through transitions involving localized states. Paper presented at the III INSEL (Incontro Nazionale sul Silicio Emettitore di Luce), Torino, 12–13 October 1995.     

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.     

The relationship between hydrogen and paramagnetic defects in thin film silicon irradiated with 2 MeV electrons

After irradiation of hydrogenated amorphous and microcrystalline silicon (a-Si:H and μc-Si:H) with 2 MeV electrons at 100 K, we observe satellite-like components close to the dominating electron spin resonance (ESR) signal of these materials. The satellites overlap with the commonly observed dangling bond resonance and are proposed to originate from a hyperfine interaction with the nuclear magnetic moment of hydrogen atoms in a-Si:H and μc-Si:H. Our present study is focused on the verification of this hypothesis. Equivalent hydrogenated and deuterated a-/μc-Si:H/D materials have been investigated with ESR before and after 2 MeV electron bombardment. From the difference between ESR spectra of hydrogenated and deuterated samples we identify the doublet structure in the ESR spectra as a hyperfine pattern of hydrogen-related paramagnetic centers. The observations of H-related paramagnetic centers in a-/μc-Si:H are of particular interest in view of metastability models of a-Si:H, which include H-related complexes as precursors for the stabilization of the metastable Si dangling bonds. The nature of the observed center is discussed in the light of known H-related complexes in crystalline Si and suggested H-related dangling bonds in a-Si:H.     

Light-induced metastable state in doping-modulated amorphous silicon superlattices

Photo-induced decrease in conductance after long light exposure has been observed for hydrogenated amorphous silicon (a-Si:H) npnp . doping-modulated superlattices showing large persistent photoconductivity (PPC). The initial increase in PPC is taken over by the decrease even to the negative PPC after long illumination. This light-induced, metastable conductance can be recovered completely by 160°C annealing, which is independent of exposure time. In particular, the metastable defects created in the p-layers are found to be annealed out at 100°C. The subband gap light exposure on the a-Si:H npnp. multilayers showing n-type conduction gives rise to the increase of conductance. On the contrary, the conductance of the multilayers having p-channel conduction decreases by IR exposure. These results strongly suggest the creation and annealing of dangling bonds by light-soaking and annealing in doping-modulated superlattices.     

Dynamics of hydrogen in hydrogenated amorphous silicon

The problem of hydrogen diffusion in hydrogenated amorphous silicon (a-Si:H) is studied semiclassically. It is found that the local hydrogen concentration fluctuations-induced extra potential wells, if intense enough, lead to the localized electronic states in a-Si:H. These localized states are metastable. The trapping of electrons and holes in these states leads to the electrical degradation of the material. These states also act as recombination centers for photo-generated carriers (electrons and holes) which in turn may excite a hydrogen atom from a nearby Si-H bond and breaks the weak (strained) Si-Si bond thereby apparently enhancing the hydrogen diffusion and increasing the light-induced dangling bonds.     

Metastability and microstructural changes in hydrogenated amorphous silicon

The effects of prolonged illumination and subsequent thermal treatment, on the valence band density of states in hydrogenated amorphous silicon have been investigated. Significant reversible changes are observed upon light soaking and annealing sequences. A microscopic model consistent with the experimental observations is proposed for the light-induced generation and thermal recovery of defects in a-Si:H.     

Surface effects on the electrical conduction of porous silicon

The electrical current of porous silicon (PS) has been measured while several treatments are made to the samples. When the samples are exposed to air, the DC current increases or decreases depending on the surface conditions of the samples. These results, found to be caused by water vapors in air, can be explained based upon the adsorbate-induced surface band bending. Photon soaking in air alters the direction of current change after air exposure and Fourier Transform Infrared Spectra show a redistribution of surface adsorbates after photon soaking in air. This indicates that photon soaking in air can cause a change in the band bending on the surface of PS.     

Effect of charged deep states in hydrogenated amorphous silicon on the behavior of iron oxides nanoparticles deposited on its surface

Langmuir-Blodgett technique has been used for the deposition of ordered two-dimensional arrays of iron oxides (Fe₃O₄/Fe₂O₃) nanoparticles onto the photovoltaic hydrogenated amorphous silicon (a-Si:H) thin film. Electric field at the a-Si:H/iron oxides nanoparticles interface was directly in the electrochemical cell modified by light soaking and bias voltage (negative or positive) pretreatment resulting in the change of the dominant type of charged deep states in the a-Si:H layer. Induced reversible changes in the nanoparticle redox behavior have been observed. We suggest two possible explanations of the data obtained, both of them are needed to describe measured electrochemical signals. The first one consists in the electrocatalytical effect caused by the defect states (negatively or positively charged) in the a-Si:H layer. The second one consists in the possibility to manipulate the nanoparticle cores in the prepared structure immersed in aqueous solution via the laser irradiation under specific bias voltage. In this case, the nanoparticle cores are assumed to be covered with surface clusters of heterovalent complexes created onto the surface regions with prevailing ferrous or ferric valency. Immersed in the high viscosity surrounding composed of the wet organic nanoparticle envelope these cores are able to perform a field-assisted pivotal motion. The local electric field induced by the deep states in the a-Si:H layer stabilizes their “orientation ordering” in an energetically favourable position.     

Study of photoconductivity and photoluminescence of organic/porous silicon complexes

In this paper, time-varying photoconductivity (PC) and the photoluminescence (PL) of different complexes were studied. Due to thick polymer layer hindering light penetrating into porous silicon (PS) layer, intrinsic PS luminescence in polymer/PS system disappeared. The physical origin of PL may be related to the recombination mechanisms involving surface defect states such as silicon oxide, siloxene. Due to carrier transfer controlled by different energy barrier, different devices prepared from different doped Si wafer showed opposite current-voltage characteristic.     

多孔硅的光生伏特效应

多孔硅(PS)的可见光致发光的发现[1],引起人们对PS的光电特性及其在光电器件上应用可能性的广泛探索.已报道用PS制成发出可见光的电致发光器件[2]及高灵敏的光探测器件[3].本文将报道PS层与金属接触,光照时能出现很强的光生伏特效应,利用这一特性有可能制成高效的光电转换器件.     

稳定、优质nc-Si/a-Si:H薄膜的研制和特性分析

利用等离子体增强化学气相沉积技术研制出了优质稳定的氢化非晶-纳米晶两相结构硅薄膜.薄膜的光电导率相对于器件质量的非晶硅有两个数量级的提高；光敏性也较好，光、暗电导比可以达到１０⁴，此外薄膜的光电导谱具有更宽的长波光谱响应.更为重要 的是薄膜的光致退化效应远小于典型的非晶硅薄膜，在光强为５０ｍW／ｃｍ²的卤钨灯光 照２４h后，光电导的衰退小于１０％.这种薄膜优良的光电性能源于薄膜中的非晶母体的存在使其在 光学跃迁中的动量选择定则发生松弛，因而具有大的光学吸收系数和 关键词： 非晶硅 微结构 光致变化     

退火对ZnS/PS复合体系光致发光特性的影响

用脉冲激光沉积(PLD)技术以多孔硅(PS)为衬底生长了ZnS薄膜,分别测量了ZnS、PS以及ZnS/PS复合体系在室温下的光致发光(PL)光谱。结果发现,ZnS/PS复合体系的PL光谱中PS的发光峰位相对于新制备的PS有所蓝移。把该ZnS/PS样品分成三块,在真空400℃分别退火10,20,30 min,研究不同退火时间对ZnS/PS复合体系光致发光特性的影响。发现退火后样品的PL光谱中都出现了一个新的绿色发光带,归结为ZnS的缺陷中心发光。随着退火时间的延长,PS的发光强度逐渐降低且峰位红移。把ZnS的蓝、绿光与PS的红光相叠加,整个ZnS/PS复合体系在可见光区450~700 nm形成一个较宽的光致发光谱带,呈现较强的白光发射。     

Excitonic photoluminescence characteristics of amorphous silicon nanoparticles embedded in silicon nitride film

We have investigated the photoluminescence (PL) properties of amorphous silicon nanoparticles (a-Si NPs) embedded in silicon nitride film (Si-in-SiN_x) grown by helicon wave plasma-enhanced chemical vapor deposition (HWP-CVD) technique. The PL spectrum of the film exhibits a broad band constituted of two Gaussian components. From photoluminescence excitation (PLE) measurements, it is elucidated that the two PL bands are associated with the a-Si NPs and the silicon nitride matrix surrounding a-Si NPs, respectively. The existence of Stokes shift between PL and absorption edge indicates that radiative recombination of carriers occurs in the states at the surface of the Si NPs, whereas their generation takes place in the a-Si NPs cores and the silicon nitride matrix, respectively. The visible PL of the film originates from the radiative recombination of excitons trapped in the surface states. At decreasing excitation energy (E_ex), the PL peak energy was found to be redshifted, accompanied by a narrowing of the bandwidth. These results are explained by surface exciton recombination model taking into account there existing a size distribution of a-Si NPs in the silicon nitride matrix.     

Light-induced metastable defects in a-Si:H as elucidated by optically detected magnetic resonance measurements at 2K

We observed a gradual increase of a nonradiative recombination channel in a-Si:H by strong light exposure at 2K, i.e., an increase in the intensity of the quenching optically detected magnetic resonance (ODMR) line at g=2.005 and no change of the other quenching lines at g=2.004 and g=2.013. The sample with previous light soaking at 300K still showed a degradation of photoluminescence (PL) efficiency as much as that for the sample without previous light soaking, but no obvious change of the quelching ODMR lines. An increase of silicon dangling bond (db) density and the other nonradiative recombination process are suggested to explain the experimental results.     

多孔硅蓝光发射与发光机制

在制备出光致发光能量为２．７ｅＶ的发射蓝光多孔硅的基础上对它进行了较系统的研究：测量了它的光致发光时间分辨光谱，用傅里叶交换红外光谱分析了其表面吸附原子的局域振动模，研究了γ射线辐照对其发光的影响，并与发红、黄光的多孔硅作了对比，通过空气中长期存放、激光和紫外线照射的方法，研究了光致发光峰能量为２．７ｅＶ的多孔硅发光稳定性．我们及其它文献中报道的多孔硅蓝光发射的实验结果与量子限制模型矛盾，但能用量子限制／发光中心模型解释．我们认为多孔硅的２．７ｅＶ发光是多孔硅中包裹纳米硅的ＳｉＯ_x层中某种特征发光中心引起的． 关键词：     

Transport and stability studies on high band gap a-Si:H films prepared by argon dilution

Device quality hydrogenated amorphous silicon films (a-Si:H) are deposited at a high deposition rate (4–5 Å/s) using a mixture of argon and hydrogen-diluted silane. The films exhibit good opto-electronic properties and show less degradation upon light soaking. Light-induced changes in conductivity could be annealed at much lower temperature. The presence of Ar^* and atomic hydrogen in plasma replaces the weak Si-Si bonds, which are responsible for light-induced degradation by strong Si-Si bonds. This results in the improved stability of the films.     

Role of heterogeneities in Staebler–Wronski effect

The effect of light soaking (LS) on the properties of hydrogenated amorphous silicon (a-Si:H) presents many challenging puzzles. We look at some of them, along with their present understanding. In particular, the role of the heterogeneities in LS is examined. We find that for most of the solved as well as unsolved puzzles, the long-range potential fluctuations arising from the heterogeneities in the films, afford an alternative view which looks quite plausible. The implications of such considerations are used to speculate on the possibility of making stable a-Si:H solar cells.     

Photo-Induced Metastable Effects in Hydrogenated Amorphous Silicon (a-Si:H)

Light induced changes of electronic properties are studied in glow discharge deposited a-Si: H-films by ESR, field effect, DLTS and electronic transport. These effects are caused by silicon dangling bonds generated by recombination processes, which raise the density of states near midgap. The concomitant increase of potential fluctuations indicates that these defects are inhomogeneously distributed.     

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。