【Solar Cell】太阳能电池的光吸收系数（Optical Absorption Coefficient）的半经验公式

【start：240806】

引言

动机

在计算半导体的光吸收系数$\alpha$时，‌需要同时考虑波长$\lambda$和温度$T$的变化，这时需要找到一个经验公式来对其进行描述。‌

For the absorption coefficient $\alpha$ of silicon we use a widely used semi-empirical model.

【ref】[1] A. Varpula and M. Prunnila, Diffusion-emission theory of photon enhanced thermionic emission solar energy harvesters, Journal of Applied Physics 112, 044506 (2012).

参考

主要的参考文献（Solar Cell）：

【ref】[1] K. Rajkanan, Absorption coefficient of silicon for solar cell calculations, (1979).
【ref】[2] K. Bücher, J. Bruns, and H. G. Wagemann, Absorption coefficient of silicon: An assessment of measurements and the simulation of temperature variation, Journal of Applied Physics 75, 1127 (1994).
【ref】[3] M. A. Green, Self-consistent optical parameters of intrinsic silicon at 300K including temperature coefficients, Solar Energy Materials and Solar Cells 92, 1305 (2008).
【ref】[4] C.-Y. Tsai, Absorption coefficients of silicon: A theoretical treatment, Journal of Applied Physics 123, 183103 (2018).

主要的参考文献（PETE）：

【ref】[1] A. Varpula and M. Prunnila, Diffusion-emission theory of photon enhanced thermionic emission solar energy harvesters, Journal of Applied Physics 112, 044506 (2012).
【ref】[2] A. Varpula, K. Tappura, and M. Prunnila, Si, GaAs, and InP as cathode materials for photon-enhanced thermionic emission solar cells, Solar Energy Materials and Solar Cells 134, 351 (2015).

光吸收简介

光吸收机理（Optical Absorption Mechanism）

半导体的光吸收过程主要涉及本征吸收和非本征吸收两种机制。‌本征吸收是指价带中的电子吸收能量大于或等于禁带宽度的光子，‌从而跃迁到导带，‌同时在价带中留下空穴，‌形成电子-空穴对。‌这个过程要求入射光子的能量（‌hν）‌至少等于材料的禁带宽度（‌Eg）‌，‌即hν≥Eg；非本征吸收则包括杂质吸收、‌自由载流子吸收等多种机制，‌这些机制与半导体的杂质浓度、‌温度等因素有关。‌

对于本征吸收，‌其吸收系数与光子能量的关系在直接跃迁的情况下可以表示为：‌$\alpha \propto (h\nu -Eg{)}^{1/2}$，其中，‌α是吸收系数，‌hν是光子能量，‌Eg是禁带宽度。‌这个公式适用于直接跃迁的半导体材料，‌如GaAs等。‌然而，‌半导体的光吸收系数不仅与波长（‌或光子能量）‌有关，‌还受到温度的影响。‌温度的变化会影响半导体的禁带宽度，‌因为禁带宽度会随着温度的升高而减小。‌这意味着，‌随着温度的升高，‌半导体的光吸收截止波长也会随之增长。‌因此，‌在实际应用中，‌计算半导体的光吸收系数时，‌需要同时考虑波长和温度的变化。‌

此外，‌非本征吸收机制，‌如杂质吸收和自由载流子吸收，‌也会影响半导体的光吸收特性。‌这些机制与半导体的杂质浓度、‌温度等因素密切相关，‌因此在具体应用中还需要考虑这些因素的影响。‌

光吸收系数（Optical Absorption Coefficient）

• Different semiconductor materials have different absorption coefficients.
• Materials with higher absorption coefficients more readily absorb photons, which excite electrons into the conduction band.
• Knowing the absorption coefficients of materials aids engineers in determining which material to use in their solar cell designs.

光吸收系数的意义：

The absorption coefficient determines how far into a material light of a particular wavelength can penetrate before it is absorbed. In a material with a low absorption coefficient, light is only poorly absorbed, and if the material is thin enough, it will appear transparent to that wavelength.

光吸收系数的依赖性：

The absorption coefficient depends on the material and also on the wavelength of light which is being absorbed. Semiconductor materials have a sharp edge in their absorption coefficient, since light which has energy below the band gap does not have sufficient energy to excite an electron into the conduction band from the valence band. Consequently, this light is not absorbed. The absorption coefficient for several semiconductor materials is shown below.

The absorption coefficient, $\alpha$, in a variety of semiconductor materials at 300K as a function of the vacuum wavelength of light.

对光吸收系数曲线的变化趋势的理解：

The above graph shows that: even for those photons which have an energy above the band gap, the absorption coefficient is not constant, but still depends strongly on wavelength. The probability of absorbing a photon depends on the likelihood of having a photon and an electron interact in such a way as to move from one energy band to another. For photons which have an energy very close to that of the band gap, the absorption is relatively low since only those electrons directly at the valence band edge can interact with the photon to cause absorption. As the photon energy increases, not just the electrons already having energy close to that of the band gap can interact with the photon. Therefore, a larger number of electrons can interact with the photon and result in the photon being absorbed.

当光子能量等于带隙时，只有价带附近的电子能被激发；然而，当光子能量比带隙大得多后，能量比价带低的那部分电子也会被激发，这时光电子的数量才会快速增加；

【ref】Absorption Coefficient

Silicon的光吸收系数

(Rajkanan, 1979) {T=20~500K}

【ref】[1] K. Rajkanan, Absorption coefficient of silicon for solar cell calculations, (1979).

【Abstract】The optical absorption coefficient is an important parameter in calculating the performance characteristics of solar cells. For silicon solar cells it is desirable to know the absorption coefficient over the range of1.1-4.0 eV and over a wide range of temperature, particularly when evaluating the concentration type systems. An analytical (empirical) expression has been developed for this purpose. We have interpreted the available experimental data in terms of three bands of silicon. With our fit, the experimental data can be explained to within an accuracy of 20% and its validity extends from 1.1 to 4.0 eV and over the temperature range of 20-500°K.

光吸收系数$\alpha$的曲线图

带隙$E_g$的半经验公式

$E_g$的温度依赖性：The variation of band gap energy is important in finding the variation of absorption coefficient with temperature.

吸收系数$\alpha$的半经验模型

半经验模型中的参数如下：

编写代码的注意事项

在编写数值模拟的代码时，需要注意：

（1）求和号$\Sigma$中含有$i$和$j$两种下标，每种下标各含两个元素，这表示需要对它们对应的4种组合项分别求和，然后相加；

（2）始终保证光子能量$h\nu$大于带隙$E$，只要某个项和$h\nu$和$E$关，那么不管是根号项还是平方项的括号里都不能出现负的能量差值；

（3）保证$kT$、$h\nu$、$E$的单位一致，例如都以电子伏特$eV$为单位；

(Bücher, 1994) {T=25~90°C}

【ref】[1] K. Bücher, J. Bruns, and H. G. Wagemann, Absorption coefficient of silicon: An assessment of measurements and the simulation of temperature variation, Journal of Applied Physics 75, 1127 (1994).

【Abstract】The absorption coefficient of crystalline silicon is an important input for designing solar cells and extracting recombination parameters from device measurements. Since many contradicting measurements have been published, an assessment of data is given based on device measurements and on the discussion of experiments in the literature. An absorption coefficient for the ultraviolet to infrared spectral range is proposed, based on the results of three groups. These data can be described semiempirically by the theory of direct and indirect band transitions. This formulation enables the determination of the optical absorption in crystalline silicon at an arbitrary temperature. The interpretation and design of solar cells for operation at temperatures above room temperature is now possible.

(Green, 2008) {T=-24~200°C}

【ref】[1] M. A. Green, Self-consistent optical parameters of intrinsic silicon at 300K including temperature coefficients, Solar Energy Materials and Solar Cells 92, 1305 (2008).

【Abstract】An updated tabulation is presented of the optical properties of intrinsic silicon, of particular interest in solar cell calculations. Improved values of absorption coefficient, refractive index and extinction coefficient at 300 K are tabulated over the 0.25-1.45 um wavelength range at 0.01 um intervals. The selfconsistent tabulation was derived from Kramers-Kronig analysis of updated reflectance data deduced from the literature. The inclusion of normalised temperature coefficients allows extrapolation over a wide temperature range, with accuracy similar to that of available experimental data demonstrated over the-24°C to 200°C range.

(Tsai, 2018) {physics-based formulas}

【ref】[1] C.-Y. Tsai, Absorption coefficients of silicon: A theoretical treatment, Journal of Applied Physics 123, 183103 (2018).

【Abstract】A theoretical model with explicit formulas for calculating the optical absorption and gain coefficients of silicon is presented. It incorporates direct and indirect interband transitions and considers the effects of occupied/unoccupied carrier states. The indirect interband transition is calculated from the secondorder time-independent perturbation theory of quantum mechanics by incorporating all eight possible routes of absorption or emission of photons and phonons. Absorption coefficients of silicon are calculated from these formulas. The agreements and discrepancies among the calculated results, the Rajkanan-Singh-Shewchun (RSS) formula, and Green’s data are investigated and discussed. For example, the RSS formula tends to overestimate the contributions of indirect transitions for cases with high photon energy. The results show that the state occupied/unoccupied effect is almost negligible for silicon absorption coefficients up to the onset of the optical gain condition where the energy separation of Quasi-Femi levels between electrons and holes is larger than the band-gap energy. The usefulness of using the physics-based formulas, rather than semi-empirical fitting ones, for absorption coefficients in theoretical studies of photovoltaic devices is also discussed.

Other Platforms

The optical properties of silicon measure at 300K. While a wide range of wavelengths is given here, silicon solar cells typical only operate from 400 to 1100 nm.

Absorption coefficient of silicon in cm-1 as a function of the wavelength. Silicon is an indirect bandgap semiconductor so there is a long tail in absorption out to long wavelengths. The data is graphed on a log scale. The drop in absorption at the band gap (around 1100 nm) is sharper than might first appear. See also absorption coefficient.

【ref】Optical Properties of Silicon

其他材料的光吸收系数

GaAs & InP

For GaAs and InP the empirical Urbach-edge model [31] and a simple empirical model for highphoton energies are combined.

【ref】[31] M. Beaudoin, A.J.G. DeVries, S.R. Johnson, H. Laman, T. Tiedje, Optical absorption edge of semi-insulating GaAs and InP at high temperatures, Appl. Phys. Lett. 70 (26) (1997) 3540–3542.

The combined model for GaAs and InP the absorption coefficient = the absorption coefficient of the Urbach-edge model + The empirical high-energy absorption coefficient

the absorption coefficient of the Urbach-edge model is given by [31]. (The Urbach-edge
model is only valid for the photon energies of the order of the band gap or below.)

The empirical high-energy absorption coefficient is given by

Photon recycling effect

Photon recycling is also neglected in the model, although it may have an effect in direct band gap semiconductors such as GaAs and InP.

InGaN

对于不同的阴极材料，吸收系数一般可以表示为：

半导体阴极材料几乎不会吸收能量低于带隙的光子，因此吸收系数为 0。A 为常数项，根据材料的变化而变化。

假设阴极厚度超过 100 μm，过剩电子浓度$\Delta n$从阴极 0.01 μm 处扩散至 1 μm 时，浓度缓慢下降，但仍处于同一数量级。电子往阴极更深处扩散，浓度出现了明显下降，在 10 μm 处降低至 1013 cm-3， 而在 100 μm 处仅剩6.56 × 107 cm-3——这说明在一定阴极厚度范围内，过剩电子浓度可以近似被看作均匀分布，但是超过这个范围后会迅速降低。因此在模拟计算中阴极厚度对过剩载流子输运特性的影响不能被忽略。

【ref】[1] 汪平安, 基于光子增强热电子发射的InGaN太阳能电池研究_汪平安.Pdf, 2023.

补充资料

The Solar Spectrum (AM1.5G)

The NREL AM1.5G spectrum (Light from the whole sky at a typical latitude), from
http://rredc.nrel.gov/solar/spectra/am1.5/

【ref】[1] Steve Byrnes, The Shockley-Queisser Limit (Mathmatica) (2012).

Direct & Indirect Band Gap Semiconductors

In a direct band gap semiconductor, the top of the valence band and the bottom of the conduction band occur at the same value of momentum, as in the schematic below

In an indirect band gap semiconductor, the maximum energy of the valence band occurs at a different value of momentum to the minimum in the conduction band energy

A photon of energy Eg, where Eg is the band gap energy, can produce an electron-hole pair in a direct band gap semiconductor quite easily, because the electron does not need to be given very much momentum.

However, an electron must also undergo a significant change in its momentum for a photon of energy Eg to produce an electron-hole pair in an indirect band gap semiconductor. This is possible, but it requires such an electron to interact not only with the photon to gain energy, but also with a lattice vibration called a phonon in order to either gain or lose momentum.

The indirect process proceeds at a much slower rate, as it requires three entities to intersect in order to proceed: an electron, a photon and a phonon. This is analogous to chemical reactions, where, in a particular reaction step, a reaction between two molecules will proceed at a much greater rate than a process which involves three molecules.

As a result of such considerations, gallium arsenide (GaAs) and other direct band gap semiconductors are used to make optical devices such as LEDs and semiconductor lasers, whereas silicon, which is an indirect band gap semiconductor, is not.

【ref】DoITPoMS \ Teaching & Learning Packages \ Introduction To Semiconductors \ Direct and Indirect Band Gap Semiconductors

Generation Rate (of the electron-hole pair)

• The generation of an electron-hole pair can be calculated at any location within the solar cell, at any wavelength of light, or for the entire standard solar spectrum.
• Generation is the greatest at the surface of the material, where the majority of the light is absorbed.
• Because the light used in PV applications contains many different wavelengths, many different generation rates must be taken into account when designing a solar cell.

从下面几张图可以看出：当吸收因子较大时，光电子几乎都是在Si的表面附近生成的；而当吸收因子较小时，Si的各深度处都有光电子的生成

【ref】Generation Rate