The optical absorption edge is a key property determining the optical emission spectrum in direct-bandgap III-V semiconductors. It reflects the influence of numerous properties including the joint optical density of states, the optical transition strength, and the presence of localized tail states at the band edges. Precise and repeatable measurement of the absorption edge is crucial for assessing material quality and provides insight to the density of states and transition probabilities in the material. Specifically, these include the fundamental bandgap energy, the magnitude of the absorption coefficient at the bandgap energy, and the characteristic width of the Urbach tail that embodies the manifestation of localized states near the band edges due to lattice disorder. Examining the absorption coefficient in terms of these model parameters provides insight into the optical joint density of states, the optical transition strength, and Coulomb enhancement of the optical transition strength. Existing models typically treat interband and tail state absorption separately, which can hinder the extraction of the bandgap energy from the absorption coefficient spectrum.
The fundamental bandgap energy of a semiconductor is defined as the energy separation between the continuum valence band maximum and continuum conduction band minimum. This definition is precise in the absence of defect or tail states that cause sub-bandgap absorption. The unavoidable presence of these localized states results in a degree of ambiguity about the determination of the bandgap energy. The bandgap energy of bulk semiconductors is at times identified as the energy at which the first derivative of the absorption coefficient α, extinction coefficient k, or imaginary part of the dielectric function £2 attains its maximum value. This so-called first derivative maximum method approximates the energy at which the joint optical density of states increases at the greatest rate. For direct-bandgap bulk semiconductors this corresponds to the onset of optical transitions involving the edges of valence and conduction band continuum states once the photon energy equals or exceeds the fundamental bandgap energy. The first derivative maximum method is also used to identify the ground state transition energy for quantum-confined structures such as quantum wells or superlattices. Nevertheless, the first derivative maximum provides little insight into the shape of the absorption edge that can be strongly influenced by the Coulomb interaction between the electrons and holes and the presence of localized states near the continuum band edges. These effects influence the fundamental bandgap energy as defined by the energy separation of the continuum band edges.
What is needed in the art is an improved model that treats interband and tail state absorption simultaneously, enabling highly accurate and repeatable measurement of the bandgap energy of direct-gap semiconductors such as GaAs, GaSb, InAs, or InSb. The improved model should also measure the Urbach energy describing the density of sub-bandgap tail states. The model should also be capable of describing absorption for any direct-gap semiconductor while making no assumptions about the energy dependence of the dipole and momentum matrix elements, one of which is commonly taken to be constant with respect to photon energy in conventional models.
In one aspect, a method for determining a characteristic of a direct-gap semiconductor comprises measuring at least one optical constant of a first sample of a direct-gap semiconductor with an optical spectrometer, calculating an estimated value of an optical parameter of the first sample of the direct-gap semiconductor based on fitting the model αg(ln(1+e(hν-E
In one embodiment, the method further comprises obtaining at least one predetermined absorption characteristic of at least one known material as the second value of the optical parameter, wherein the characteristic of the direct-gap semiconductor is a composition of the direct-gap semiconductor, and wherein the optical parameter is an absorption characteristic. In one embodiment, the model is fit using a least-squares fitting algorithm to measured optical absorption curves over a range spanning three times Eu of the direct-gap semiconductor below the bandgap energy to 0.2 eV above the bandgap energy.
In one embodiment, the method further comprises the steps of measuring at least one optical constant of a second sample of a direct-gap semiconductor with the optical spectrometer, and determining a second amplitude of an absorption knee of the second sample as the second value of the optical parameter, based on fitting the model αg(ln(1+e(hν-E
In one embodiment, the model is fit using a least-squares fitting algorithm to measured optical absorption curves over a range spanning three times Eu of the direct-gap semiconductor below the bandgap energy to 0.2 eV above the bandgap energy. In one embodiment, the method further comprises the steps of measuring at least one optical constant of a second sample of a direct-gap semiconductor with the optical spectrometer, and determining a second Urbach energy parameter of the second sample as the second value of the optical parameter, based on fitting the model αg(ln(1+e(hν-E
In one embodiment, the model is fit using a least-squares fitting algorithm to measured optical absorption curves over a range spanning three times Eu of the direct-gap semiconductor below the bandgap energy to 0.2 eV above the bandgap energy. In one embodiment, the direct-gap semiconductor comprises a material selected from the group consisting of Ga, As, In, and Sb.
In one aspect, a method for determining a temperature of a direct-gap semiconductor comprises measuring at least one optical constant of a sample of a direct-gap semiconductor with an optical spectrometer, determining a bandgap energy of the sample based on fitting the model αg(ln(1+e(hν-E
In one embodiment, the model is fit using a least-squares fitting algorithm to measured optical absorption curves over a range spanning three times Eu of the direct-gap semiconductor below the bandgap energy to 0.2 eV above the bandgap energy. In one embodiment, the absorption characteristic is the bandgap energy. In one embodiment, the direct-gap semiconductor comprises a material selected from the group consisting of Ga, As, In, and Sb.
In one aspect, a system for determining a characteristic of a direct-gap semiconductor comprises a spectroscopic device configured to measure at least one optical constant of a sample of a direct-gap semiconductor, a computing device communicatively connected to the spectroscopic device, comprising a processor and a non-transitory computer-readable medium with instructions stored thereon, which when executed by a processor, perform steps comprising calculating an estimated value of an optical parameter of the first sample of the direct-gap semiconductor based on fitting the model αg(ln(1+e(hν-E
In one embodiment, the system further comprises an optical coupling medium positioned between the spectroscopic device and the sample of the direct-gap semiconductor. In one embodiment, the steps further comprise obtaining at least one predetermined absorption characteristic of at least one known material as the second value of the optical parameter, wherein the characteristic of the direct-gap semiconductor is a composition of the direct-gap semiconductor, and wherein the optical parameter is an absorption characteristic.
In one embodiment, the model is fit using a least-squares fitting algorithm to measured optical absorption curves over a range spanning three times Eu of the direct-gap semiconductor below the bandgap energy to 0.2 eV above the bandgap energy. In one embodiment, the absorption characteristic is the bandgap energy.
In one embodiment, the steps further comprise measuring at least one optical constant of a second sample of a direct-gap semiconductor with the optical spectrometer, and determining a second amplitude of an absorption knee of the second sample as the second value of the optical parameter, based on fitting the model αg(ln(1+e(hν-E
The foregoing purposes and features, as well as other purposes and features, will become apparent with reference to the description and accompanying figures below, which are included to provide an understanding of the invention and constitute a part of the specification, in which like numerals represent like elements, and in which:
It is to be understood that the figures and descriptions of the present invention have been simplified to illustrate elements that are relevant for a more clear comprehension of the present invention, while eliminating, for the purpose of clarity, many other elements found in devices, systems and methods for characterizing direct-gap semiconductors. Those of ordinary skill in the art may recognize that other elements and/or steps are desirable and/or required in implementing the present invention. However, because such elements and steps are well known in the art, and because they do not facilitate a better understanding of the present invention, a discussion of such elements and steps is not provided herein. The disclosure herein is directed to all such variations and modifications to such elements and methods known to those skilled in the art.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, the preferred methods and materials are described.
As used herein, each of the following terms has the meaning associated with it in this section.
The articles “a” and “an” are used herein to refer to one or to more than one (i.e., to at least one) of the grammatical object of the article. By way of example, “an element” means one element or more than one element.
“About” as used herein when referring to a measurable value such as an amount, a temporal duration, and the like, is meant to encompass variations of ±20%, ±10%, ±5%, ±1%, and ±0.1% from the specified value, as such variations are appropriate.
Ranges: throughout this disclosure, various aspects of the invention can be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the invention. Where appropriate, the description of a range should be considered to have specifically disclosed all the possible subranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed subranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 2.7, 3, 4, 5, 5.3, and 6. This applies regardless of the breadth of the range.
In some aspects of the present invention, software executing the instructions provided herein may be stored on a non-transitory computer-readable medium, wherein the software performs some or all of the steps of the present invention when executed on a processor.
Aspects of the invention relate to algorithms executed in computer software. Though certain embodiments may be described as written in particular programming languages, or executed on particular operating systems or computing platforms, it is understood that the system and method of the present invention is not limited to any particular computing language, platform, or combination thereof. Software executing the algorithms described herein may be written in any programming language known in the art, compiled or interpreted, including but not limited to C, C++, C#, Objective-C, Java, JavaScript, Python, PHP, Perl, Ruby, or Visual Basic. It is further understood that elements of the present invention may be executed on any acceptable computing platform, including but not limited to a server, a cloud instance, a workstation, a thin client, a mobile device, an embedded microcontroller, a television, or any other suitable computing device known in the art.
Parts of this invention are described as software running on a computing device. Though software described herein may be disclosed as operating on one particular computing device (e.g. a dedicated server or a workstation), it is understood in the art that software is intrinsically portable and that most software running on a dedicated server may also be run, for the purposes of the present invention, on any of a wide range of devices including desktop or mobile devices, laptops, tablets, smartphones, watches, wearable electronics or other wireless digital/cellular phones, televisions, cloud instances, embedded microcontrollers, thin client devices, or any other suitable computing device known in the art.
Similarly, parts of this invention are described as communicating over a variety of wireless or wired computer networks. For the purposes of this invention, the words “network”, “networked”, and “networking” are understood to encompass wired Ethernet, fiber optic connections, wireless connections including any of the various 802.11 standards, cellular WAN infrastructures such as 3G or 4G/LTE networks, Bluetooth®, Bluetooth® Low Energy (BLE) or Zigbee® communication links, or any other method by which one electronic device is capable of communicating with another. In some embodiments, elements of the networked portion of the invention may be implemented over a Virtual Private Network (VPN).
Referring now in detail to the drawings, in which like reference numerals indicate like parts or elements throughout the several views, in various embodiments, presented herein are devices, systems and methods utilizing an improved optical absorption model for direct-gap semiconductors.
In its textbook form, the optical absorption spectrum of a semiconductor is expressed as a product of the joint optical density of states ρ(hν) (cm−3·eV−1) and a transition strength S(hν) (cm2·eV) with
α(hν)=ρ(hν)·S(hν) Equation 1
The joint optical density of states depends on the electron and hole density of states, which are determined by the band structure in the vicinity of the fundamental bandgap. For direct-gap semiconductors, such as III-V binaries, electrons and holes have approximately parabolic band dispersion near the band edges. The corresponding joint optical density of states exhibits a square root dependence on photon energy hν, with
where me is the free electron mass, and mc and mν are the dimensionless effective masses of the conduction band electrons and valence band holes, respectively. In the absence of strain the light hole and heavy hole bands are degenerate at the Γ point, and the joint optical density of states is dominated by the smaller electron effective mass. Here ρ(hν) is the density of states in the absence of band filling effects, such as the Moss-Burstein shift and bandgap renormalization. These effects are negligible for measurements where the photoexcited carrier concentration is well below degeneracy.
The transition strength in Equation 1 can be expressed in terms of a dimensionless transition strength S0(hν) with
where h is Planck's constant, c is the speed of light, E0 is the vacuum permittivity, e is the electron charge, and n(hν) is the refractive index that typically has a weak dependence on photon energy. The absorption coefficient changes by orders of magnitude in the vicinity of the band edge of the materials disclosed herein, while the refractive index changes by less than 2% and as such is assumed to be an average constant value.
The transition strength S0 describes the probability of a given optical transition and is described by the optical perturbation to the crystal Hamiltonian due to the presence of light. According to Fermi's golden rule the rate of optical transitions is proportional to the perturbed Hamiltonian matrix element for interband transitions. In the long-wavelength dipole approximation where the wavelength of the perturbing optical field is much greater than the unit cell, the transition strength associated with this matrix element is equivalently related to either the momentum matrix element ψh|p|ψe or dipole matrix element ψh|r|ψe as
In practice, either the momentum matrix element, dipole matrix element, or transition strength is assumed to be a constant that is independent of photon energy in much of the analyses performed in the literature. The assumption that any one of these three is constant assumes an energy dependence for the other two. Using Equation 1 through Equation 4, the absorption coefficient is expressed in terms of the momentum matrix element ψh|p|ψe in Equation 5A, the dipole matrix element ψh|r|ψe in Equation 5B, and the product of the two in Equation 5C.
By writing the equations in this form, the photon energy dependence of each of the three assumptions is explicitly shown. In addition to the square root density states term, the constant momentum matrix element approximation results in a one over energy term, the constant dipole matrix element results in a linear energy term, and the constant transition strength approximation has no additional energy dependent term. The choice of which is taken to be constant influences the interpretation of the behavior of the absorption coefficient above the bandgap energy.
This treatment of the absorption edge considers only the continuum states involved in transitions at and above the fundamental bandgap energy and does not account for free exciton absorption, the Coulomb enhancement of absorption near the bandgap, or the broadening effects of thermal and frozen in crystal lattice disorder. Even high-quality materials exhibit an Urbach absorption edge that is mainly due to the electron-phonon interaction. Excitonic absorption is a significant effect in high purity material, particularly at low temperatures, and results in absorption peaks below the bandgap energy.
Furthermore, the Coulomb interaction between free electrons and holes results in an enhancement of absorption near the bandgap that is dependent on the free exciton binding energy that typically scales with bandgap energy in the III-Vs. The Coulomb interaction is a multi-particle phenomenon involving both an electron and hole and as such cannot be treated within the free electron band structure framework, but rather requires the addition of the electron-hole Coulomb potential to the crystal Hamiltonian. Thus the Coulomb interaction can modify both the density of states and the transition strength. The effect of the Coulomb interaction is large near the bandgap energy and asymptotically approaches unity at energies above the bandgap energy, which has been quantified by an enhancement factor described as
The exciton binding energy Eex scales with bandgap energy and is experimentally determined as 4.0 meV for GaAs, 2.1 meV for GaSb, 1.0 meV for InAs, and 0.4 meV for InSb. As such, the Coulomb enhancement of absorption is expected to increase with bandgap energy.
A model is disclosed that in one embodiment evaluates the onset of absorption at the fundamental bandgap and that encompasses the asymptotic behaviors of the absorption coefficient above and below the bandgap. The model is shown in Equation 7A and Equation 7B and contains 5 parameters: the bandgap energy Eg, determined by the behavior of the absorption coefficient above bandgap; the characteristic Urbach energy Eu, based on the slope of the absorption tail below the bandgap; the magnitude of the absorption coefficient at the bandgap energy αy; and the power law dependence p(hν) of the absorption coefficient above the bandgap that is comprised of a constant term pg that describes the power law at the bandgap and a photon energy hν dependent term that describes the variation in the power law above the bandgap with characteristic energy, Em.
For energies above the bandgap, hν>Eg, the asymptotic behavior reflects optical absorption involving continuum states and is specified as a power law with
For energies below the bandgap, hν≤Eg, the asymptotic behavior reflects optical absorption involving localized tail states specified by an exponential Urbach tail with
α(hν)=αg(ln 2)−p(hν)e(hν-E
where the right-hand approximation is valid for abrupt absorption edges, with Eu<<Em.
Examining the absorption coefficient in terms of these model parameters provides insight into the optical joint density of states, the optical transition strength, and Coulomb enhancement of the optical transition strength. As an example, the parabolic single-electron band model predicts a square root density of states with power law one half and an Urbach tail width that approaches zero. The model in Equation 7 does not describe bound exciton absorption peaks when present in the data, which would be modeled by an additional function.
The model is shown in
Although knowledge of the absorption coefficient at the bandgap energy is useful, it does not fully describe the overall magnitude of the absorption near the bandgap that is strongly influenced by the Coulomb interaction in addition to the density of states. For instance, the effective cutoff wavelength of a photodetector is typically shorter than the bandgap wavelength, as thin film materials can be transparent right at the bandgap. Therefore a better figure of merit for comparing the optical absorption strength of different materials for device applications is the “knee” of the absorption spectrum when viewed on a log scale, which identifies the magnitude of the absorption coefficient as it rolls over above the bandgap. The position of the absorption spectrum knee Ek is specified by the energy where the radius of curvature ra of the absorption spectrum has a minimum value
with
Here x=hν/α and y=ln(α(hν)/b) are the dimensionless energy and absorption coefficient normalized by the constants a with units of energy and b with units of inverse length. The parameter b does not appear in Equation 10 as the derivatives of y are independent of the vertical scale when the absorption coefficient is observed on a log scale. The parameter a scales the horizontal energy axis to the energy range of interest, as the range selected affects the observed energy position of the knee. The first and second derivatives are x′=1/a, y′=α′/α, x″=0, and y″=α″/α−(α′/α)2. The radius of curvature of ln(α(hν)) exhibits a single well-defined minimum that is observed above the bandgap energy E9, thus defining the position Ek and amplitude αk of the knee in the absorption spectrum.
The absorption edge also manifests itself in the imaginary parts of the complex index of refraction, ñ=n+ik, and the complex dielectric function, {tilde over (ε)}=ε1+iε2, as is apparent in the following relationships between the optical constants.
As such the absorption edge model in Equation 7 is also suitable for examination of the extinction coefficient k and the imaginary dielectric coefficient ε2.
The first derivative method of identifying bandgap energy finds the energy where the absorption edge increases at the greatest rate. Numerical calculation of the derivative at each data point is performed by the center-difference formula
where f is the measured discrete data as a function of energy, which is either the absorption coefficient α, the extinction coefficient k, or the imaginary dielectric coefficient ε2. If the energy spacing of the data is constant, the denominator hν[j+1]−hν[j−1] may be replaced by 2Δhν, where Δhν is the constant energy spacing. The center-difference point-by-point derivative calculation does not shift of the maximum of the first derivative, unlike backward or forward difference formulas that shift the derivative by ±Δhν, respectively.
Embodiments of the invention rely on a model that treats interband and tail state absorption simultaneously, enabling highly accurate and repeatable measurement of the bandgap energy of direct-gap semiconductors such as GaAs, GaSb, InAs, or InSb. The Urbach energy describing the density of sub-bandgap tail states is also measured. The model may be used to describe absorption for any direct-gap semiconductor and makes no assumptions about the energy dependence of the dipole and momentum matrix elements, one of which is commonly taken to be constant with respect to photon energy in conventional models.
Embodiments of the invention utilize a five parameter model formulated to describe the key characteristics of the optical absorption edge of direct bandgap semiconductors. These parameters include the bandgap energy, based on the behavior of the absorption coefficient above bandgap; the characteristic Urbach energy, based on the width of the absorption tail below the bandgap; the magnitude of the absorption coefficient at the bandgap energy, and the power law dependence of the absorption coefficient above the bandgap. The power law is comprised of a constant term that describes the power law at the bandgap and a photon energy dependent term that describes variations in the power law above the bandgap using a characteristic energy. The model provides highly accurate and repeatable measurements of the bandgap energy of direct-gap semiconductors, in addition to providing insight to material quality via the Urbach energy, which quantifies the impact of sub-bandgap tail states, and the absorption knee amplitude. The model is simple and easily applied to any direct-gap semiconductor, enabling direct comparison between materials systems. The power law fit parameters provide insight to the energy dependence of the interband matrix element and the strength of the Coulomb enhancement of absorption. Finally, a well-defined absorption “knee” exists which may be calculated from the fitted model parameters and serves as a useful figure of merit for material quality.
Embodiments of the invention utilize a mathematical algorithm which is fit to measured optical absorption curves for direct bandgap semiconductors. It describes absorption (units of inverse cm) as a function of photon energy (eV) and is given in Equation 7A and Equation 7B above, where αg is the absorption amplitude (inverse cm), hν is the photon energy, Eg is the bandgap energy, Eu is the Urbach energy, and p is an energy-dependent power law term. Functionally, p is equal to pg+(hν−Eg)/Em, where pg is a constant power law term and Em is a characteristic energy describing the above-bandgap absorption. In one embodiment, the model is fit using a least-squares fitting algorithm to measured absorption curves over a range spanning approximately 0.020 eV below the bandgap energy to 0.175 eV above the bandgap.
Certain embodiments and examples disclosed herein may reference particular fit ranges, however it is understood that the fit range may be subjective and that the presented examples are in no way limiting of the systems and methods disclosed herein. As would be understood by one skilled in the art, the fit range used will vary from material to material. In some embodiments, the fit range includes data points at several times the Urbach energy (En) below the bandgap energy, and data points up to about 0.2 eV above the bandgap energy. In various embodiments, a lower bound of a suitable fit range may be 0.02 eV below the bandgap energy, 0.03 eV below the bandgap energy, 0.04 eV below the bandgap energy, 0.05 eV below the bandgap energy, two times the material's Eu, below the bandgap energy, three times the material's Eu, below the bandgap energy, four times the material's Eu, below the bandgap energy, five times the material's Eu, below the bandgap energy, or any other suitable lower bound. In some embodiments, an upper bound of a suitable fit range may be 0.05 eV above the bandgap energy, 0.1 eV above the bandgap energy, 0.15 eV above the bandgap energy, 0.175 eV above the bandgap energy, 0.2 eV above the bandgap energy, 0.225 eV above the bandgap energy, 0.25 eV above the bandgap energy, 0.3 eV above the bandgap energy, 0.4 eV above the bandgap energy, or any suitable upper bound. In some embodiments, some points within the disclosed fit range may be excluded from the fit, for example to omit higher energy features not included in the disclosed models of the fundamental absorption edge.
With reference now to
Embodiments of the invention are directed to a system or method for determining the composition of a material having unknown composition, based on the measured temperature of the material and the bandgap energy. The temperature may be measured directly, for example using a thermometer, thermal couple, or the like. In some embodiments, where measurements are performed at room temperature, the sample temperature may be assumed to be equal to that of the environment, for example between 295 K and 297 K for typical laboratory environments.
With reference now to
The optical constants of the sample 302 may be calculated by a computing device 305 including for example an acquisition engine 306 communicatively connected to spectroscopic device 304. The acquisition engine 306 may be configured to receive data from spectroscopic device 304 either as calculated values or as measured primitives from which the optical constants may be calculated. Optical constants that may be obtained by the acquisition engine include, but are not limited to, Absorption (α), the extinction coefficient (κ), or the imaginary dielectric constant (ε2). The computing system 305 may then use the measured constants to generate a fitted bandgap energy plot, using the equation αg (ln(1+e(hν-E
Further, embodiments of the invention can be used as an optical thermometer, as the bandgap energy is also temperature dependent. If the temperature dependence of the bandgap energy of a sample material is known, then measurements of the bandgap energy can determine the sample's temperature. With reference now to
With reference now to
The optical constants of the sample 502 may be calculated by a computing device 505 including for example an acquisition engine 506 communicatively connected to spectroscopic device 504. The acquisition engine 506 may be configured to receive data from spectroscopic device 504 either as calculated values or as measured primitives from which the optical constants may be calculated. The computing system 505 may then use the measured constants to generate a fitted bandgap energy plot, using the equation αg (ln(1+e(hν-E
Embodiments of the invention can be used to directly compare optical quality of sample materials through the amplitude of the absorption knee. Higher optical quality samples will exhibit higher amplitude at the absorption knee. With reference now to
With reference now to
The optical constants of the sample 702 may be calculated by a computing device 705 including for example an acquisition engine 706 communicatively connected to spectroscopic device 704. The acquisition engine 706 may be configured to receive data from spectroscopic device 704 either as calculated values or as measured primitives from which the optical constants may be calculated. The computing system 705 may then use the measured constants to generate a fitted bandgap energy plot, using the equation αg (ln(1+e(hν-E
With reference now to
The optical constants of the sample 712 may be calculated by a computing device 715 including for example an acquisition engine 716 communicatively connected to spectroscopic device 714. The acquisition engine 716 may be configured to receive data from spectroscopic device 714 either as calculated values or as measured primitives from which the optical constants may be calculated. The computing system 715 may then use the measured constants to generate a fitted bandgap energy plot, using the equation αg (ln(1+e(hν-E
Exemplary fit models and corresponding absorption knees are shown in
The invention is now described with reference to the following Examples. These Examples are provided for the purpose of illustration only and the invention should in no way be construed as being limited to these Examples, but rather should be construed to encompass any and all variations which become evident as a result of the teaching provided herein.
Without further description, it is believed that one of ordinary skill in the art can, using the preceding description and the following illustrative examples, make and utilize the present invention and practice the claimed methods. The following working examples therefore, specifically point out the preferred embodiments of the present invention, and are not to be construed as limiting in any way the remainder of the disclosure.
The fundamental absorption-edge of semi-insulating GaAs and unintentionally doped GaSb, InAs, and InSb was investigated using spectroscopic ellipsometry. The measurements were performed on commercially available III-V wafers. The material specifications for resistivity, Hall mobility, and carrier concentration supplied by the manufacture are summarized in Table 1. The carrier concentrations were well below the conduction and valence band effective density of states Nc and Nν at room temperature. Therefore the material was not degenerate and band filling effects such as the Moss-Burstein shift were negligible. The absorption measurements were performed on three separate GaAs samples A, B, and C to assess the reproducibility of the measurement technique and modeling work.
Table 1 below shows the physical and electrical characteristics of III-V substrates studied by ellipsometry. Values were obtained from wafer datasheets.
The spectroscopic ellipsometry measurements of GaAs and GaSb were performed using a J. A. Woollam VASE spectroscopic ellipsometer that covered 0.39 to 6.42 eV (193 to 3200 nm wavelength). Measurements of InAs and InSb were performed using a J. A. Woollam IR-VASE ellipsometer that covered 0.04 to 0.73 eV (1.7 to 30 μm). All measurements were performed at room temperature (297 K) using four incident angles (68°, 72°, 76°, and 80°) with a spectral resolution of 3.9 nm (6.3 meV for GaAs and 1.7 meV for GaSb) for the VASE measurements and 16 cm′ (2.0 meV for InAs and InSb) for the IR-VASE measurements. Because the wafers were transparent below the bandgap energy, reflection from the backside of the wafer resulted in the collection of spurious depolarized light at the detector. Therefore, the wafer backsides were roughened sequentially with 320 and 400 grit sandpaper to diffusely scatter the backside reflections. After backside roughening, the depolarization was less than 2%.
The WVASE software was used to obtain the optical constants of III-V wafers from the measured ellipsometry parameters W and A. The ellipsometry optical model employed two layers, a surface oxide layer and the III-V layer. The thickness of the wafers ranged from 350 to 640 μm and was treated as infinite when analyzing ellipsometry data. This assumption was justified as light that reaches the backside of the substrate was diffusely scattered. Optical constants of the oxide layers and the initial values of optical constants of the III-V substrates were provided by the WVASE software library. Because the optical constants for InSb oxide were not available, the InSb native oxide was modeled using the GaSb oxide optical constants.
The best fit thickness of the oxide layers is shown in Table 2 below. The optical constants were determined using the wavelength-by-wavelength method of analysis, which provided raw data that was not distorted by any mathematical modeling of the optical constants.
The Kramers-Kronig consistency of the optical constants was verified by repeating the fits using a generalized oscillator; the optical constants derived from the wavelength-by-wavelength fitting and generalized oscillator model agreed to within less than 1% over the entire wavelength range.
The measured absorption spectra for semi-insulating GaAs sample A and undoped GaSb, InAs, and InSb are presented in
With reference to
The optical constants n and k, and E1 and E2, are shown for the three semi-insulating GaAs samples in
The GaAs bandgap energy was estimated by i) fitting the absorption model in Equation 7 to a, k, and ε2, ii) finding the first derivative maximum of α, k, and ε2, and iii) finding the peak values of n and ε1, shown in Table 4 below. There was excellent agreement between the three GaAs samples with the average and standard deviation of the values of the three samples shown in the right-hand column.
Table 4 above shows the GaAs bandgap energy determined by first derivative maximum of extinction coefficient k, absorption coefficient α, and imaginary dielectric function E2. Also shown are bandgap energies determined from the maximum values of refractive index n and real dielectric function ε1. The model parameters for α, k, and ε2 are summarized for each GaAs sample in the lower portion of the table. The model fits were performed over the same photon energy range as in
Agreement was observed for the best fit model (Equation 7) parameters for the bandgap energy Eg and the Urbach energy Eu obtained from the three optical constants α, k, and ε2. Agreement was also observed for the first derivative maximum obtained from the three optical constants α, k, and £2, although the first derivative maximum values were about 2 meV less than the bandgap value determined from the fit of the model to the data. The best fit power law pg values were within 4% across the 3 sets of optical constants. The characteristic energy Em was larger for the optical constants k and ε2, indicating a weaker energy dependence above the bandgap compared to the absorption coefficient α, as indicated in the relations of Equation 11 where k and E2 are proportional to α/hν.
The absorption amplitude was observed to increase with bandgap energy and was analyzed at the bandgap energy using the product of the optical density of states, the transition strength, and the Coulomb enhancement factor in Equation 2, Equation 3, and Equation 6, where
The exciton binding energy Eex is a product of the band structure and can be expressed to first order in terms of the effective mass as
where ε is the dimensionless static dielectric constant and RH=13.6 eV is the hydrogen Ryberg constant. The four terms on the right-hand side of Equation 13 vary with bandgap energy and their values and power law relation with bandgap energy are provided in Table 5 below.
Experimentally measured exciton binding energies from the literature were used in the calculation of Equation 13, as the values predicted by Equation 14 were significantly larger for the smaller bandgap materials.
Table 5 shows material parameters and calculated absorption amplitude at the bandgap energy. The power law relation of the parameters with bandgap energy and reduced effective mass are shown in the rightmost two columns.
The experimental values of the joint optical density of states effective mass, the exciton binding energy Eex, and the strength of the Coulomb interaction √{square root over (Eex)} all increased with bandgap energy with power laws 1.08, 1.11, and 0.56 respectively. The transition strength S0 decreased with bandgap energy with power law-0.95. The index of refraction was about 9% larger for the antimonides and did not significantly vary with bandgap energy. The momentum matrix element (2/me)|h|p|ψe|2 in units of eV and the subsequent transition strength was determined from literature. The momentum matrix element at the F point did not significantly change with bandgap energy.
The theoretical absorption amplitude αA (black circles) and the experimental absorption amplitudes α9 (red squares) and absorption knee αk (blue diamonds) are compared in
With reference to
The Kramers-Kronig dispersion relation between the real and imaginary parts of the optical constants specified that onset of absorption in the imaginary parts, k, or ε2, is manifested as a peak in the real part, n or ε1. This small peak in the real part of the optical constants is denoted as Δn and ΔE1 and is given by Kramers-Kronig relation of the optical constants k and ε2 evaluated over an integration range of hν1=1.38 eV to hν2=1.50 eV, with
where denotes the Cauchy principal value of the integral. The integration range of 1.38 eV to 1.50 eV was selected to yield the same amplitude of Δn as in the experiment. This integration range yielded an amplitude for Δε1 that was within 5% of the experimental value. The experimental values for Δn and ΔE1 were obtained from the measured data by subtracting off a linear background not attributed to the fundamental absorption edge, which was n=2.930+0.469·hν and ε1=8.178+3.352·hν for GaAs. It was necessary to subtract the linear background as it resulted in a blue shift of the peak values that was not attributable to the fundamental bandgap. Decreasing the lower limit of integration below 1.38 eV had no effect on the amplitude or peak position of Δn and ΔE1 due to the rapid decrease in optical absorption below the fundamental absorption edge. However, increasing the upper limit of integration above 1.50 eV increased the amplitude and slightly blue-shifted the peaks in relation to the bandgap energy, which was as much as 0.9 meV for an upper integration limit of 2.50 eV. The integration range of 1.38 eV to 1.50 eV was in agreement with other analyses performed in literature.
The semi-insulating GaAs bandgap energies at 297 K determined by the various methods discussed in this work are compared in
With reference to
The energy position of the first derivative maximum Ep of the absorption model in Equation 7 as a function of the power law parameter pg is shown in
With reference to
The ratio of the model parameters Em/Eg as a function of pg is shown in red in
With reference to
The exciton binding energies in the III-V semiconductors examined in this example ranged from approximately 0.4 meV for InSb to 4.0 meV for GaAs, which were relatively small compared to the thermal energy of 25.6 meV at the 297 K measurement temperature. Nevertheless, an exciton absorption peak was typically observed in high-purity GaAs up to room temperature. However, the semi-insulating GaAs measured in this example had a very short carrier lifetime due to a high density of deep-levels in the material. Therefore an excitonic absorption peak was not observed in the spectroscopic ellipsometry measurements in this example, although the Coulomb interaction was clearly present in the onset of absorption of GaAs, GaSb, and InAs.
For small bandgap InSb where the Coulomb enhancement of absorption was weak, it was straightforward to interpret the model parameters pg=0.495 and Em=4.33 eV. In the absence of a Coulomb interaction, the power law reduces to the dispersion relation between energy and momentum determined by band structure near the fundamental bandgap. In the nearly free carrier approximation this yielded a value of one half corresponding to a parabolic band. Furthermore, the relatively large value of the characteristic energy Em indicated that the optical transition strength S0 was close to constant.
The Coulomb enhancement of absorption was significant for GaAs, GaSb, and InAs and complicated the physical interpretation of the model parameters pg and Em. Nevertheless, they provided insight to the relative strength of Coulomb interaction and the energy dependence of transition strength. The increase in the magnitude of the Coulomb interaction with bandgap was evident from the decrease in the power law pg as the absorption at the bandgap energy was enhanced. Furthermore, a picture emerged where the photon energy dependence of the optical transition as a function of bandgap energy was clarified. The decrease in Em/Eex with bandgap energy associated with the optical transition indicates that as the Coulomb interaction increased, the photon energy dependence changed from a constant transition strength (Equation 5C) for small bandgap InSb to a constant dipole matrix element (Equation 5B) for larger bandgap GaAs.
None of the experimental observations in these materials indicated that the momentum matrix element was independent of photon energy, which was expected to result in negative values for the characteristic energy Em. However, in Table 5 the theoretical momentum matrix values at the F point were nearly constant across the materials examined, which is consistent with the experiment as illustrated by the similar power laws in the increase of absorption magnitude with bandgap energy observed in
A literature survey of the published values of the room-temperature (297 K) bandgap energy of GaAs found a range of 1.422 to 1.436 eV, with a widely accepted value of 1.424 eV. The model in Equation 7 used in this example identifies the 297 K GaAs bandgap energy at 1.418 eV, approximately 6 meV lower than the commonly-accepted value from literature. Existing studies identify the bandgap energy by backing out the Coulomb interaction from a measured feature in the optical constants or by extrapolating the below-bandgap Urbach edge to a known bandgap absorption coefficient. On the other hand, in this disclosure the bandgap is identified directly from onset of absorption in the measured optical constants, which may be better described as the optical bandgap.
When comparing the features in the GaAs optical constants measured in this example to those in the literature, the energy of the onset of absorption and the peak in the index of refraction were at the same energy positions. This indicates that any discrepancy was not due to experimental measurement differences, such as temperature or doping level, but instead was a result of how the bandgap was determined from the optical constants, such as how the onset of absorption was impacted by the Coulomb interaction. There is a distinction between the single-electron bandgap, a theoretical construct based on the assumption of empty conduction band that neglects many-body effects, and the optical bandgap energy that includes the effects of electron-electron interactions and electron-hole interactions, encompassing excitonic absorption and the Coulomb interaction. These effects result in a smaller optical bandgap than that predicted from the single-electron model.
The optical bandgap energy is the most relevant consideration in the description and design of optoelectronic devices, as it is the energy of the onset of absorption and emission that determines how devices perform. For example, the bandgap energy is generally described as the cutoff of absorption in photodetectors and photovoltaic solar cells and as the cutoff of emission from light emitting diodes.
Somewhat closer agreement was found between the GaSb, InAs, and InSb bandgap energies measured in this example and those reported in the literature. A literature survey finds 297 K bandgap energies ranging from 0.724 to 0.728 eV for GaSb, from 0.350 to 0.356 eV for InAs, and from 0.169 to 0.180 eV for InSb. The optical bandgap energies measured in this example were 0.730 eV, 0.357 eV, and 0.180 eV for GaSb, InAs, and InSb respectively, which were all on the upper end of the range measured in the literature. Many of these measurements were based on analysis of photoluminescence peak energy or extrapolations of absorption coefficients down to zero. There are complications in the extraction of optical bandgap energy using each of these various methods which can make it difficult to exactly compare the room temperature bandgap energy.
The absorption model presented is in principle applicable to any direct-gap semiconductor or material that exhibits an exponential absorption edge, such as III-V, II-VI, I-VII, and their alloys. Application to very small bandgap materials operating in the long-wave infrared would be subject to the typical challenges associated with narrow-bandgap materials, such as free carrier absorption and degenerate carrier levels. Furthermore, for materials with strong excitonic absorption, it would be necessary to add a term to capture the excitonic lineshape. This may become a significant effect for high purity materials with bandgaps wider than GaAs. Ionic materials and highly mismatched alloys are expected to exhibit a broader absorption edge and with a subsequent larger Urbach energy Eu. Moreover, alloy-induced inhomogeneous broadening of the absorption edge will complicate the interpretation of the modeled bandgap energy.
The intrinsic absorption edges of GaAs, GaSb, InAs, and InSb were examined using a model that was developed to describe and parameterize the experimentally observed features of the fundamental bandgap absorption edge, which include the optical bandgap energy Eg, the width of the Urbach tail Eu, the impact of the Coulomb interaction on the absorption edge pg, and the magnitude of the absorption coefficient at the bandgap cutoff α9 and at the knee of the absorption spectrum αk. The Urbach parameter Eu was determined from the exponential absorption edge below the bandgap and the optical bandgap parameter E9 and absorption edge power law parameter p9 were determined from the above-bandgap absorption. The room-temperature (297 K) values of the optical bandgap energy and Urbach parameter were 1.418 eV and 8.7 meV for GaAs, 0.730 eV and 14.0 meV for GaSb, 0.357 eV and 14.1 meV for InAs, and 0.180 eV and 10.7 meV for InSb. The GaAs optical bandgap energy determined from the absorption coefficient, extinction coefficient, and real part of the dielectric function agreed closely with the peak values of the refractive index and real dielectric function. The energy dependence of the optical absorption above the bandgap was observed to be most accurately described by the constant dipole matrix element approximation for GaAs where the Coulomb interaction was strong and by the constant transition strength approximation for InSb where the Coulomb interaction was weak.
With reference now to
The corresponding graphs of the extinction coefficient (K) and imaginary dielectric coefficient (ε2) are shown in
The disclosures of each and every patent, patent application, and publication cited herein are hereby incorporated herein by reference in their entirety. While this invention has been disclosed with reference to specific embodiments, it is apparent that other embodiments and variations of this invention may be devised by others skilled in the art without departing from the true spirit and scope of the invention.
The following publications are each incorporated herein by reference in their entireties:
C. Ghezzi, R. Magnanini, A. Parisini, B. Rotelli, L. Tarricone, A. Bosacchi, and S. Franchi, “Optical absorption near the fundamental absorption edge in Gasb”, Phys. Rev. B 52, 1463 (1995).
E. O. Kane, “Band Structure of Indium Antimonide”, J. Phys. Chem. Solids 1, 249 (1957).
This application claims priority to U.S. Provisional Patent Application No. 62/890,324, filed on Aug. 22, 2019, incorporated herein by reference in its entirety.
This invention was made with government support under 1410393 awarded by the National Science Foundation. The government has certain rights in the invention.
Number | Date | Country | |
---|---|---|---|
62890324 | Aug 2019 | US |