WO2011111853A1 - 光電変換装置及びその特性検査方法 - Google Patents
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- WO2011111853A1 WO2011111853A1 PCT/JP2011/055882 JP2011055882W WO2011111853A1 WO 2011111853 A1 WO2011111853 A1 WO 2011111853A1 JP 2011055882 W JP2011055882 W JP 2011055882W WO 2011111853 A1 WO2011111853 A1 WO 2011111853A1
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- H01S5/30—Structure or shape of the active region; Materials used for the active region
- H01S5/34—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers
- H01S5/343—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser
- H01S5/34333—Structure or shape of the active region; Materials used for the active region comprising quantum well or superlattice structures, e.g. single quantum well [SQW] lasers, multiple quantum well [MQW] lasers or graded index separate confinement heterostructure [GRINSCH] lasers in AIIIBV compounds, e.g. AlGaAs-laser, InP-based laser with a well layer based on Ga(In)N or Ga(In)P, e.g. blue laser
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- H01L33/26—Materials of the light emitting region
- H01L33/30—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table
- H01L33/32—Materials of the light emitting region containing only elements of Group III and Group V of the Periodic Table containing nitrogen
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Definitions
- the present invention relates to a photoelectric conversion device and a characteristic inspection method thereof, and more particularly to a photoelectric conversion device capable of suppressing characteristic deterioration due to crystal defects and a method of detecting a crystal defect inherent in the photoelectric conversion device.
- light-emitting elements such as light-emitting diodes and semiconductor lasers
- light-receiving elements such as solar cells
- FIG. 8 is a block diagram illustrating a configuration of the photoelectric conversion element 100 as an example, and includes an n-type semiconductor layer 101, an active layer (photoelectric conversion unit) 102 formed on the n-type semiconductor layer 101, and the active layer. And a p-type semiconductor layer 103 formed on the substrate 103, and these are formed as a basic structure of a photoelectric conversion device by a known semiconductor manufacturing technique or the like.
- the photoelectric conversion element may include a crystal defect (threading dislocation) 201 as shown in FIG. 8 due to the incomplete structure of the semiconductor crystal.
- FIG. 8 schematically shows a crystal defect inherent in a semiconductor crystal constituting the photoelectric conversion element 100, and a threading dislocation 201 and a non-luminescent center 202 exist.
- threading dislocations 201 that are generated at the interface between the growth substrate and the growth layer and propagate from below to the photoelectric conversion element 100 behave as non-luminescent centers 202 that inhibit photoelectric conversion in the active layer 102.
- threading dislocations are usually included at a high density of 1 ⁇ 10 8 cm ⁇ 2 to 1 ⁇ 10 10 cm ⁇ 2 , which is a major obstacle to improving the performance of light-emitting elements.
- Patent Documents 1 and 2 listed below are techniques for reducing the influence of this crystal defect.
- Patent Documents 1 and 2 belong to a crystal growth technique called selective growth or lateral growth for those skilled in the art.
- This lateral growth process requires a surface processing process such as mask formation accompanying normal crystal growth. This leads to an increase in the number of processes, which causes problems in terms of yield and manufacturing cost.
- the present invention has been made in view of such circumstances, and provides a photoelectric conversion device that suppresses deterioration of characteristics due to crystal defects without increasing the number of manufacturing steps, and a method for detecting crystal defects inherent in the photoelectric conversion device.
- the purpose is to do.
- the photoelectric conversion device includes a photoelectric conversion unit and a dislocation inactive unit included in the photoelectric conversion unit.
- the dislocation inactive part may be formed so as to include a crystal defect.
- the dislocation inactive part may have a photoelectric conversion function.
- the photoelectric conversion device may further include a first conductive part formed on the dislocation inactive part and a second conductive part formed under the dislocation inactive part.
- the conducting portion may have a first band gap energy
- the second conducting portion may have a second band gap energy
- the dislocation inactive portion may have a third band gap energy
- the third band gap energy may be It may be smaller than either of the first and second band gap energies.
- the photoelectric conversion device includes a first In x Ga y Al 1-xy N layer having a first conductivity type and a first In x Ga y Al 1-xy N layer.
- the In x Ga y Al 1-xy N photoelectric conversion unit and the In x Ga y Al 1-xy N photoelectric conversion unit are formed, and the second In x Ga y Al of the second conductivity type is formed.
- comprising a 1-x-y N layer, a, x and y range from 0 ⁇ x, a y ⁇ 1, in x Ga y Al 1-x-y N photoelectric conversion unit, an InN transposition inactive portion Have.
- the InN dislocation inactive part may have a layer thickness of 2 molecular layers or less.
- the InN dislocation inactive part may be formed so as to include a crystal defect.
- the method for detecting a crystal defect of a photoelectric conversion device includes a first In x Ga y Al 1-xy N layer having a first conductivity type, a first In x Ga y Al 1-xy
- the In x Ga y Al 1-xy N photoelectric conversion unit formed on the N layer and the In x Ga y Al 1-xy N photoelectric conversion unit formed of the second conductivity type are formed on the In x Ga y Al 1-xy N photoelectric conversion unit.
- the xy N photoelectric conversion unit includes an InN dislocation detection unit, and the InN dislocation detection unit is formed so as to include crystal defects, and detects crystal defects based on light emission characteristics from the InN dislocation detection unit. This is a crystal defect detection method.
- the InN dislocation detection unit may have a layer thickness of two or less molecular layers.
- the crystal defect may be detected based on cathodoluminescence from the InN dislocation detection unit.
- FIG. 1 is a block diagram showing a configuration example of a photoelectric conversion apparatus 10 according to the first embodiment of the present invention.
- a photoelectric conversion device 10 includes an n-type gallium nitride (hereinafter referred to as “n-GaN”) layer 11, a photoelectric conversion unit (Active layer) 12 formed on the n-GaN layer 11, and a photoelectric conversion device.
- n-GaN n-type gallium nitride
- p-GaN p-type gallium nitride
- a dislocation inactive unit 14 included in the photoelectric conversion unit 12 are configured and are well-known. It is formed by semiconductor manufacturing technology.
- nitride-based semiconductors have almost no suitable growth substrate, crystal defects such as threading dislocations generated from the interface between the n-GaN layer 11 and the substrate (not shown) are formed when the photoelectric conversion element 10 is formed. 21 is contained at a high density of about 1 ⁇ 10 8 cm ⁇ 2 to 1 ⁇ 10 10 cm ⁇ 2 .
- the n-GaN layer 11 is used for transporting electrons
- the p-GaN layer 13 is used for transporting holes. Therefore, the resistivity and the layer thickness of each of the n-GaN layer 11 and the p-GaN layer 13 are suitably adjusted from the viewpoint of carrier transport / collection.
- the photoelectric conversion unit 12 converts injected electrons-holes into light through a recombination process, and in the case of a light receiving element, converts the absorbed light into electrons-holes.
- the photoelectric conversion unit 12 includes, for example, gallium nitride (GaN), indium gallium nitride (InGaN), or indium nitride (InN), and includes the n-GaN layer 11.
- the p-GaN layer 13 is preferably configured to have a forbidden band width (bandgap energy) smaller than any of the p-GaN layer 13.
- the dislocation inactive part 14 will be described.
- the dislocation inactive part 14 is an InN ultrathin film
- the photoelectric conversion part 12 is described using an example of GaN.
- InN When InN is epitaxially grown on GaN, for example, when c-plane growth is performed, InN and GaN have a lattice mismatch of about 11%, so that high-density crystal defects are newly introduced during crystal growth. Will be introduced. This crystal defect significantly deteriorates the conversion efficiency in the photoelectric conversion element.
- the present inventors have found that if InN is less than or equal to a bimolecular layer (2 ML), elastic deformation is maintained without introducing crystal defects and coherent growth is possible with respect to GaN as a base.
- the ultra-thin film InN When the ultra-thin film InN is inserted into the photoelectric conversion unit 12, a quantum well structure having the ultra-thin film InN as a well layer and GaN as a barrier layer is formed. That is, the ultra-thin InN quantum well layer may function as a part of the photoelectric conversion unit 12.
- FIG. 3 shows a sample in which a quantum well structure composed of an ultra-thin InN (1ML-InN) well layer and a GaN layer whose layer thickness is controlled to a single molecular layer is grown on a GaN underlayer.
- CL image The result (CL image) of having performed cathodoluminescence (CL) observation of is shown.
- CL observation refers to irradiating an accelerated electron beam from the sample surface and performing fluorescence spectroscopic measurement from the sample.
- Vacc of the accelerating electron beam By controlling the acceleration voltage Vacc of the accelerating electron beam, the penetration depth of the electron beam can be controlled, and light emission distribution information of a desired layer structure region (depth position) can be obtained.
- FIG. 3 shows respective CL images when the observation region is 19 ⁇ 19 ⁇ m 2 and the acceleration voltage Vacc is changed in the same visual field.
- the acceleration voltages Vacc of 3 kV, 6 kV, 14 kV, and 18 kV correspond to electron beam penetration lengths of 48 nm, 160 nm, 710 nm, and 1100 nm, respectively. That is, when the acceleration voltage Vacc is 3 kV and 6 kV, the emission distribution mainly from the 1ML-InN quantum well is observed, and when the acceleration voltage Vacc is 14 kV and 18 kV, the emission distribution mainly from the GaN underlayer is observed. .
- white contrast corresponds to a light emitting region
- black contrast corresponds to a non-light emitting region (non-light emitting center), that is, a crystal defect 21 is present.
- the ultrathin film InN is formed in an island shape having a surface coverage of less than 1.
- the region illustrated by the circular frame as a mark is relatively brighter than the surroundings. It can be understood that the quantum well structure is formed only in the region and the emission intensity is improved. That is, it is considered that the ultrathin film InN is selectively grown so as to include the crystal defect 21 and has an island structure as shown in FIG.
- the dislocation inactive layer 14 does not necessarily have to be a continuous film having a surface coverage of 1, and even in an island shape including the crystal defects 21, that is, in a configuration with a surface coverage of less than 1, the crystal defects 21.
- the non-luminous property due to can be eliminated.
- FIG. 5 is a block diagram showing a configuration example of the photoelectric conversion device 30 which is an application example 1 according to the first embodiment of the present invention.
- a photoelectric conversion device 30 includes an n-type aluminum gallium nitride (hereinafter, n-AlGaN) layer 31, a photoelectric conversion unit (Active layer) 32 formed on the n-AlGaN layer 31, and the photoelectric conversion.
- n-AlGaN n-type aluminum gallium nitride
- p-AlGaN p-AlGaN
- the photoelectric conversion unit 32 is made of, for example, gallium nitride (GaN), aluminum gallium nitride (AlGaN), or aluminum indium gallium nitride (AlInGaN), and more than any of the n-AlGaN layer 31 and the p-AlGaN layer 33. It is preferable to be configured to have a small forbidden bandwidth (band gap energy).
- the dislocation inactive part 34 is composed of an ultrathin film InN.
- the n-AlGaN layer 31 is used for transporting electrons.
- the p-AlGaN layer 33 is used for transporting holes. Therefore, the resistivity and the layer thickness of the n-AlGaN layer 31 and the p-AlGaN layer 33 are each suitably adjusted in order to efficiently transport carriers.
- the photoelectric conversion unit 32 converts the injected electron-holes into ultraviolet light through a recombination process.
- the dislocation inactive part 34 suppresses the non-light emission center and increases the efficiency of the ultraviolet LED.
- the photoelectric conversion unit 32 is AlGaN
- the emission wavelength of the ultraviolet LED is shortened.
- the Al composition of AlGaN increases, the difficulty of crystal growth becomes more significant, and the density of crystal defects 21 included in the photoelectric conversion device 30 also increases. Therefore, the light emission efficiency is deteriorated.
- the ultra-thin film InN is inserted into the photoelectric conversion part 32, as shown in FIG. 3, the non-luminous property due to the crystal defect 21 is reduced. That is, in the photoelectric conversion device 30 that is an ultraviolet LED, the dislocation inactive portion 34 is configured by the ultrathin film InN, so that deterioration of the light emission efficiency accompanying the shortening of the light emission wavelength can be suppressed.
- the crystal defect 21 is inherent in the photoelectric conversion unit 32 of the photoelectric conversion device 30, the characteristic deterioration due to the crystal defect 21 can be suppressed.
- FIG. 6 is a block diagram showing a configuration example of a photoelectric conversion device 40 which is an application example 2 according to the first embodiment of the present invention.
- a photoelectric conversion device 40 includes an n-type indium gallium nitride (hereinafter referred to as n-InGaN) layer 41, a photoelectric conversion unit (Active layer) 42 formed on the n-InGaN layer 41, and the photoelectric conversion.
- the p-type indium gallium nitride (hereinafter referred to as p-InGaN) layer 43 formed on the part 42 and the dislocation inactive part 44 included in the photoelectric conversion part 42 are formed by a known semiconductor manufacturing technique or the like. Is done.
- the photoelectric conversion unit 42 is made of, for example, indium nitride (InN), indium gallium nitride (InGaN), or aluminum indium gallium nitride (AlInGaN), and is more than any of the n-InGaN layer 41 and the p-InGaN layer 43. It is preferable to be configured to have a small forbidden bandwidth (band gap energy).
- the dislocation inactive part 44 is composed of an ultrathin film InN.
- the n-InGaN layer 41 is used for transporting electrons.
- the p-InGaN layer 43 is used for transporting holes. Accordingly, the resistivity and the layer thickness of the n-InGaN layer 41 and the p-InGaN layer 43 are each suitably adjusted in order to efficiently transport carriers.
- the photoelectric conversion unit 42 converts the injected electron-holes into light through a recombination process.
- the dislocation-inactive portion 44 suppresses the non-emission center and increases the efficiency of the green laser and the red-infrared wavelength region LED.
- the photoelectric conversion unit 42 is InGaN
- the emission wavelengths of the green laser and the red-infrared wavelength region LED are lengthened.
- the In composition of InGaN increases, the difficulty of crystal growth becomes more remarkable, and the density of crystal defects 21 included in the photoelectric conversion device 40 also increases. Therefore, the light emission efficiency is deteriorated.
- the ultra-thin film InN is inserted into the photoelectric conversion unit 42, as shown in FIG. 3, the non-luminous property due to the crystal defect 21 is reduced. That is, in the photoelectric conversion device 40 that is a green laser and a red-infrared wavelength region LED, the dislocation inactive portion 44 is configured by the ultrathin film InN, thereby suppressing the deterioration of the light emission efficiency due to the longer emission wavelength. be able to.
- FIG. 7 is a block diagram showing a configuration example of a photoelectric conversion device 50 which is an application example 3 according to the first embodiment of the present invention.
- a photoelectric conversion device 50 includes an n-type aluminum indium gallium nitride (hereinafter referred to as n-AlInGaN) layer 51, a photoelectric conversion unit (Depletion layer) 52 formed on the n-AlInGaN layer 51, and the photoelectric conversion device.
- n-AlInGaN n-type aluminum indium gallium nitride
- p-AlInGaN p-AlInGaN
- the photoelectric conversion unit 52 is made of, for example, gallium nitride (GaN), indium gallium nitride (InGaN), aluminum indium nitride (AlInN), or aluminum indium gallium nitride (AlInGaN), and the n-AlInGaN layer 51 and p-AlInGaN.
- the layer 53 is preferably configured to have a forbidden band width (band gap energy) smaller than any of the layers 53.
- the dislocation inactive part 54 is composed of the ultrathin film InN.
- the n-AlInGaN layer 51 is used for transporting electrons.
- the p-AlInGaN layer 53 is used for transporting holes. Therefore, the resistivity and the layer thickness of the n-AlInGaN layer 51 and the p-AlInGaN layer 53 are each suitably adjusted from the viewpoint of carrier transport and concentration.
- the photoelectric conversion unit 52 converts the absorbed light into electron-holes.
- the dislocation inactive portion 54 improves the junction characteristics of the solar cell and increases the efficiency of the nitride solar cell.
- the photoelectric conversion unit 52 is InGaN
- the dislocation inactivation effect due to the crystal defects 21 is exhibited as shown in FIG. That is, in the photoelectric conversion device 50 that is a solar cell, the dislocation inactive portion 54 is configured by the ultrathin film InN, so that a decrease in conversion efficiency due to deterioration of the junction characteristics of the solar cell can be suppressed.
- the growth mechanism of ultra-thin InN is a self-ordered and self-stopping process by supplying excess InN than the designed film thickness and evaporating / desorbing on the growth surface.
- InN is pinned in the region where the crystal defect exists, it is considered that the evaporation / desorption rate is suppressed as compared with the region not including the crystal defect.
- the ultra-thin film InN is grown as a fractional layer InN only in a region where crystal defects exist.
- the fractional layer InN means that the surface coverage is 1 or less.
- the 0.5 molecular layer is an island structure having a one-layer thickness and a surface coverage of 50%, that is, a quantum disk structure.
- observation means by a transmission electron microscope or pit (etch pit) detection by an etching process is known. Is also complicated.
- C cathodoluminescence
- the ultrathin film InN is formed so as to include the crystal defect 21 by inserting the ultrathin film InN into the photoelectric conversion unit 12 in the photoelectric conversion device 10, and the dislocation detection unit exhibits the light emission characteristics. 15 can be used.
- the crystal defect 21 is inherent in the photoelectric conversion unit 12 of the photoelectric conversion device 10, the crystal defect 21 is easily detected by observing the dislocation detection unit 15.
- product inspection of the photoelectric conversion device 10 can be simplified.
- the ultra-thin film InN is composed of one layer.
- the present invention is not limited to this.
- a configuration in which multiple layers are inserted is also possible.
- the layer including nitride sandwiching the photoelectric conversion portion has conductivity, and can be expressed as a first conductive portion and a second conductive portion, respectively.
- the first conductive portion and the second conductive portion can be expressed as In x Ga y Al 1-xy N layers, respectively.
- the first conductive portion is represented by the first conductive type In x Ga y Al 1-1.
- the xy N layer and the second conductive part can be expressed as a second conductivity type In x Ga y Al 1-xy N layer.
- x and y may be the same or different, and the ranges of x and y may be 0 ⁇ x and y ⁇ 1.
- the photoelectric conversion unit can be expressed as an In x Ga y Al 1-xy N layer.
- each of the first conduction unit, the second conduction unit, and the photoelectric conversion unit has band gap energy, and the band gap energy (third band gap energy) of the third conduction unit. ) Is preferably smaller than either the band gap energy of the first conduction part (first band gap energy) or the band gap energy of the second conduction part (first band gap energy).
- the photoelectric conversion device can be used for light-emitting elements and light-receiving elements corresponding to ultraviolet-infrared light, particularly solar cells.
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Abstract
Description
図1は、本願発明の第1実施形態に係る光電変換装置10の構成例を示すブロック図である。図1において、光電変換装置10は、n型窒化ガリウム(以下、「n-GaN」という。)層11と、n-GaN層11上に形成される光電変換部(Active layer)12と、光電変換部12上に形成されるp型窒化ガリウム(以下、「p-GaN」という。)層13と、光電変換部12に含まれる転位不活性部14と、を有して構成され、周知の半導体製造技術などで形成される。なお窒化物系半導体では、適当な成長基板が殆ど存在しないことから、光電変換素子10を構成する場合、n-GaN層11と基板(図面省略)との界面から発生する貫通転位などの結晶欠陥21を1×108cm-2から1×1010cm-2程度と高密度に含む。
窒化物半導体による光電変換素子の第1の応用として、紫外波長域での発光ダイオード(LED)が注目されている。特に、GaNのバンド端波長である365nmより短波長領域では、発光波長の短波長化に伴い、発光効率が急激に劣化する。ここでは、超薄膜InNの非発光中心抑制効果による、紫外LEDの高効率化について説明する。
窒化物半導体による光電変換素子の第2の応用として、緑色レーザーおよび赤色-赤外波長域での発光ダイオード(LED)が注目されている。特に、500
nmより長波長領域では、発光波長の長波長化に伴い、発光効率が急激に劣化する。ここでは、超薄膜InNの非発光中心抑制効果による、緑色レーザーおよび赤色-赤外波長域LEDの高効率化について説明する。
窒化物半導体による光電変換素子の第3の応用として、広い太陽光スペクトルに対応する太陽電池が注目されている。特に、窒化物半導体は、高密度の結晶欠陥を含むため、太陽電池の接合特性が粗悪である。ここでは、超薄膜InNの転位不活性効果による、窒化物太陽電池の高効率化について説明する。
第1実施形態では、超薄膜InNによる転位不活性部の作用・効果について述べた。ところで、図3に示されている実験結果を、別の視点で解釈を与えると、超薄膜InNは転位検出部15として利用できることがわかる。以下、超薄膜InNによる転位検出部15の作用・効果について説明する。
Claims (10)
- 光電変換部と、
前記光電変換部に含まれる転位不活性部と、を備える光電変換装置。 - 前記転位不活性部は、結晶欠陥を含むように形成される請求項1に記載の光電変換装置。
- 前記転位不活性部は、光電変換機能を有する請求項1に記載の光電変換装置。
- 前記転位不活性部上に形成される第1伝導部と、
前記転位不活性部下に形成される第2伝導部と
を備え、
前記第1伝導部は第1バンドギャップエネルギーを有し、
前記第2伝導部は第2バンドギャップエネルギーを有し、
前記転位不活性部は第3バンドギャップエネルギーを有し、
前記第3バンドギャップエネルギーは前記第1および前記第2バンドギャップエネルギーのいずれかよりも小さい請求項1に記載の光電変換装置。 - 第1伝導型からなる第1InxGayAl1-x-yN層と、
前記第1InxGayAl1-x-yN層上に形成されるInxGayAl1-x-yN光電変換部と、
前記InxGayAl1-x-yN光電変換部上に形成され、第2伝導型からなる第2InxGayAl1-x-yN層と、
を備える光電変換装置であって、
前記xおよびyの範囲は0≦x,y≦1であり、
前記InxGayAl1-x-yN光電変換部は、InN転位不活性部を有する光電変換装置。 - 前記InN転位不活性部は、層厚が2分子層以下である請求項5に記載の光電変換装置。
- 前記InN転位不活性部は、結晶欠陥を含むように形成される請求項5に記載の光電変換装置。
- 第1伝導型からなる第1InxGayAl1-x-yN層と、
前記第1InxGayAl1-x-yN層上に形成されるInxGayAl1-x-yN光電変換部と、
前記InxGayAl1-x-yN光電変換部上に形成され、第2伝導型からなる第2InxGayAl1-x-yN層と、
を備える光電変換装置の結晶欠陥検出方法であって、
前記xおよびyの範囲は0≦x,y≦1であり、
前記InxGayAl1-x-yN光電変換部は、InN転位検出部を有し、
前記InN転位検出部は、結晶欠陥を含むよう形成され、
前記InN転位検出部からの発光特性に基づいて、結晶欠陥を検出する結晶欠陥検出方法。 - 前記InN転位検出部は、層厚が2分子層以下である請求項8に記載の結晶欠陥検出方法。
- 前記InN転位検出部からのカソードルミネッセンスに基づいて、結晶欠陥を検出する請求項8に記載の結晶欠陥検出方法。
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