CN102931271A - Triple-junction solar cell and preparation method thereof - Google Patents

Triple-junction solar cell and preparation method thereof Download PDF

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Publication number
CN102931271A
CN102931271A CN201210406609XA CN201210406609A CN102931271A CN 102931271 A CN102931271 A CN 102931271A CN 201210406609X A CN201210406609X A CN 201210406609XA CN 201210406609 A CN201210406609 A CN 201210406609A CN 102931271 A CN102931271 A CN 102931271A
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battery
layer
solar cell
quantum dot
thickness
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刘建庆
林志东
蔡文必
林桂江
丁杰
毕京峰
宋明辉
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Tianjin Sanan Optoelectronics Co Ltd
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Tianjin Sanan Optoelectronics Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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Abstract

The invention provides a quantum dot solar cell structure with an indium gallium arsenide (InGaAs) stress modulation layer structure and a preparation method of the quantum dot solar cell structure. By the invention, the dimension uniformity of each layer of quantum dots in a multilayer quantum dot structure is effectively controlled, so band gaps of all layers of quantum dots are basically the same, the conversion loss of photon-generated carriers between the quantum dots of different dimensions is reduced, the spectral response of the quantum dot structure is improved, the transition loss of the quantum dots is reduced, the short-circuit current of a triple-junction cell is improved, and the photoelectric conversion efficiency of a multi-junction solar cell is improved.

Description

Three-joint solar cell and preparation method thereof
Technical field
The present invention relates to a kind of high efficiency multijunction solar cell manufacturing technology, belong to technical field of semiconductor.More specifically, the present invention relates to a kind of III with epitaxially grown lamination quantum-dot structure-V family many pn junction p ns solar cell.
Background technology
The GaInP/InGaAs/Ge three-junction solar battery, because the epitaxial loayer Lattice Matching, epitaxial growth is simple, is one of at present the most frequently used multijunction solar cell structure.Because three junction batteries are series connection, so electric current is by the battery limitation of electric current minimum in three junction batteries, this has just caused the electric current of each knot battery not mate, the band gap combination of three junction batteries of Lattice Matching is 1.85eV/1.41eV/0.67eV, this will cause end battery to absorb a large amount of light, and electric current is limited by middle battery or top battery, therefore, traditional GaInP/InGaAs/Ge three-junction solar battery structure is not the combination of efficiency optimization, is difficult to the three junction battery efficient that reach best.In order to improve the electric current of three junction batteries, obtain best battery efficiency, the solar spectrum absorption region of battery during GaInP/InGaAs/Ge Lattice Matching three junction batteries need to be expanded, its mainly realization approach have in methods such as middle battery insertion quantum-dot structure, insertion quantum well structures.Wherein InAs quantum dot that middle battery PN junction knot face inserts low band gaps with expansion in the ABSORPTION EDGE of battery be proved to be practicable technology path.But, general InAs quantum dot all obtains by the S-K growth pattern, this quantum dot has nucleation site and time characteristics at random, therefore the InAs quantum dot size that obtains is difficult to control, owing to have the quantum dot of different size in the same epitaxial loayer, be applied to and occur electronics and hole in the active area of battery and be transformed into phenomenon the spatia zonularis quantum dot from the large band gap quantum dot, thereby cause a large amount of losses of photo-generated carrier, the spectral response that this will seriously reduce the middle battery with quantum-dot structure finally reduces the conversion efficiency of battery.
Summary of the invention
Goal of the invention of the present invention is that the traditional three junction battery electric currents of solution do not mate, there are the problems such as spectral response is poor, active area quantum dot lack of homogeneity in insertion InAs quantum-dot structure in middle battery.
The invention provides a kind of quantum dot solar battery structure and preparation method of the InGaAs of having stress modulation layer structure, it effectively controls the dimensional homogeneity of every layer of quantum dot in the multiple layer hetero quantum point structure, make the band gap of every layer of quantum dot basic identical, reduce the conversion loss of photo-generated carrier between the different size quantum dot, thereby improve the spectral response of quantum-dot structure, reduce the transition loss between quantum dot, promote three junction battery short circuit currents, thereby further improve the multijunction solar cell photoelectric conversion efficiency.
According to a first aspect of the invention: a kind of multijunction solar cell with quantum-dot structure, comprise end battery, middle battery and top battery, it is characterized in that: described middle battery comprises InxGa1-xAs stress modulation layer, and be grown in InAs lamination quantum-dot structure on the stress modulation layer, the In component is greater than 0.01 in the described InxGa1-xAs stress modulation layer, and thickness is lower than its critical thickness.Under the InGaAs stress modulation, InAs lamination quantum dot has arranges characteristics orderly, size uniform, can effectively reduce the efficient decay that is brought by the quantum dot size lack of homogeneity.
In the present invention, preferably, battery of the described end is the Ge battery, and middle battery is the In with the Ge Lattice Matching 0.01Ga 0.99As battery, top battery are the GaInP battery that mates with middle battery; In middle battery, described In xGa 1-xAs stress modulation layer is that the In component is 0.1 ~ 0.6 InGaAs thin layer, and thickness is lower than its critical thickness, can be 10-100nm, and the surface has formed the height relief fabric; Described InAs lamination quantum-dot structure is the multiple layer hetero quantum point structure that InAs quantum dot and InGaAs strained layer form, wherein In xGa 1-xThe In component x of As cap rock is 0.05-0.5.
According to a second aspect of the invention, the manufacture method of three-joint solar cell, it comprises the step that forms end battery, middle battery and top battery, wherein said middle battery comprises following step by lower mask body: epitaxial growth InxGa1-xAs stress modulation layer, the In component is greater than 0.01 InGaAs layer, and thickness is lower than its critical thickness; Form lamination InAs quantum dot knot at described stress modulation layer, it is comprised of InAs quantum dot and InxGa1-xAs cap rock.
More specifically, aforementioned manufacture method comprises following step: 1) a growth substrate is provided, forms end battery thereon; 2) on battery of the described end, form in battery, it comprises InxGa1-xAs stress modulation layer, and self assembly InAs lamination quantum-dot structure, described InxGa1-xAs stress modulation layer is for being lower than its critical thickness, the In component is between 0.1 ~ 0.6, described InAs lamination quantum-dot structure is formed on the InxGa1-xAs stress modulation layer, is comprised of InAs quantum dot and InGaAs cap rock, and wherein the In component of InGaAs cap rock is greater than 0.01; 3) on described middle battery, form the top battery.
In certain embodiments, described growth substrates is the Ge substrate, by battery at the bottom of epitaxial growth Ge on this substrate, or uses diffusion method battery at the bottom of this substrate forms Ge; Described middle battery is the InGaAs battery, and described top battery is the GaInP battery.
In certain embodiments, the step that forms described middle battery comprises following step: epitaxial growth back surface field layer and base on end battery; Grow by InGaAs stress modulation layer in described base; At described stress modulation layer surface deposition InAs quantum dot layer, at described InAs quantum dot layer surface coverage InGaAs, repeated growth InAs quantum dot obtains multilayer InAs self-assembled quantum dots structure; In the described InAs self-assembled quantum dots molecular structure emitter region of growing.
Preferably, the growth rate of InGaAs is 0.1～10nm/s in the described InGaAs stress modulation layer, thickness is 10～100nm, InGaAs stress modulation layer since with middle battery InGaAs mismatch, thickness is lower than its critical thickness simultaneously, has height relief fabric thin layer because Stress Release will form the surface; Described InAs quantum dot layer is grown on the InGaAs stress modulation layer of surface height fluctuating, the preferred nucleation of InAs quantum dot is in the rat position under stress modulation, thereby has size uniform, the characteristics that positional alignment is orderly, the InGaAs cap rock can effectively prevent subsiding of quantum dot on InAs quantum dot layer surface coverage, guarantee the dimensional homogeneity of quantum dot, repeated growth InAs quantum dot and InGaAs cap rock just can obtain the lamination quantum-dot structure of size uniform, wherein the growth rate of quantum dot is 0.01～5 ML/s, and thickness is 1.5～4 monoatomic layers.Especially, behind the described InAs quantum dot of epitaxial growth molecular layer, can introduce growth interruption to strengthen atomic migration, the growth interruption time is 5～100 seconds.
Beneficial effect of the present invention: 1) compare with conventional GaInP/InGaAs/Ge three junction batteries, can effectively expand the spectral response of battery among the InGaAs, improve the short circuit current of three junction batteries, improve the currents match of three junction batteries, reach higher conversion efficiency.2) than conventional quantum dot cell, can reduce by the inhomogeneous charge carrier that causes of quantum dot size compoundly, improve minority carrier life time, thereby increase the Carriers Absorption ability, final raising efficiency.
Other features and advantages of the present invention will be set forth in the following description, and, partly from specification, become apparent, perhaps understand by implementing the present invention.Purpose of the present invention and other advantages can realize and obtain by specifically noted structure in specification, claims and accompanying drawing.
Description of drawings
Accompanying drawing is used to provide a further understanding of the present invention, and consists of the part of specification, is used for together with embodiments of the present invention explaining the present invention, is not construed as limiting the invention.In addition, the accompanying drawing data are to describe summary, are not to draw in proportion.
Fig. 1 is according to three-junction solar battery structural representation of the invention process.
Each label represents among the figure:
The 100:Ge substrate;
The 110:GaInP Window layer;
200:In 0.01Ga 0.99The As resilient coating;
300: tunnel junctions of the middle end;
310:AlGaAs back surface field layer;
320:In 0.01Ga 0.99The As base;
330:In 0.15Ga 0.85As stress modulation layer;
340:InAs/In 0.15Ga 0.85As lamination quantum dot layer;
341:In 0.15Ga 0.85The As cap rock;
The 342:InAs quantum dot;
350:In 0.01Ga 0.99The As emitter region;
The 360:AlInP Window layer;
400: tunnel junctions in the top;
500:GaInP top battery;
600:GaAs block a shot the layer.
Embodiment
The invention will be further described below in conjunction with embodiment, but should not limit protection scope of the present invention with this.
As shown in Figure 1, a kind of three-joint solar cell comprises: battery 100, In at the bottom of the Ge 0.01Ga 0.99Battery and Ga among the As 0.5In 0.5P top battery 500 couples together by tunnel junctions 500,510 between each knot battery.
Battery 100 forms by self-diffusion on P type Ge substrate at the bottom of the Ge.In MOCVD equipment, lead in advance PH 3And growth GaInP initiation layer can make the P atom be diffused in the Ge substrate, forms N-type Ge emitter region, and emitter region thickness is about 0.1um.
Growth GaInP 110 on the battery 100 at the bottom of the Ge, to overcome the lattice mismatch of Ge substrate and InGaAs material, the while is as the Window layer of battery at the bottom of the Ge.
At GaInP Window layer 110 In that grows 0.01Ga 0.99As resilient coating 200, to obtain smooth epitaxial surface, thickness is 1000nm.
Connect with tunnel junctions 300 between resilient coating and the middle battery.Tunnel junctions 300 is the heavy doping PN junction, is comprised of N-shaped and the heavily doped GaAs of p-type, AlGaAs material, and doping content is 1 * 10 19Cm -3-3 * 10 22Cm -3Between, thickness is between 10～30 nm.
Battery is by back surface field layer 310, In among the InGaAs 0.01Ga 0.99As p-i-n structure, and Window layer 360 forms.Back surface field layer 310 is generally the AlGaAs material, and Window layer 360 is the materials such as GaInP, AlGaInP or AlInP.In 0.01Ga 0.99The In that mixes for Zn in the P district of As p-i-n structure (base 320) 0.01Ga 0.99The As material, doping content is 1 * 10 16Cm -3--3 * 10 18Cm -3Between; N district (emitter region 350) is Si doping In 0.01Ga 0.99As, doping content is 1 * 10 17Cm -3-3 * 10 19Cm -3The i district is by In xGa 1-xAs stress modulation layer 330 and InAs/InGaAs lamination quantum dot 340 form, wherein In xGa 1-xThe In component of As stress modulation layer is between 0.1-0.6, and thickness is 10-100nm, is lower than its critical thickness.After stress modulation layer 330 extension are finished, growth InAs quantum-dot structure 342, the InAs quantum dot will mainly be formed on In under stress modulation xGa 1-xAs stress modulation layer rat position, behind the InAs quantum dot of having grown, growth In xGa 1-xThe As cap rock, In xGa 1-xThe In component of As cap rock is between 0.05-0.5, and thickness is lower than its critical thickness, is generally between the 10-50nm, and repeatedly repeated deposition InAs/InGaAs quantum dot layer just can obtain the lamination quantum-dot structure.Quantum dot by the method formation, because stress modulation effect and multilayer precipitation, the dimensional homogeneity of this quantum dot is good, can establishment InAs quantum dot because the poor electronics that causes of dimensional homogeneity and hole are transformed into phenomenon the spatia zonularis quantum dot from the large band gap quantum dot, the spectral response of battery in the lifting finally improves the photoelectric conversion efficiency of battery.
Connect by tunnel junctions 400 between middle battery and the top battery 500.Tunnel junctions 400 can be selected heavily doped n+-GaAs/p+-AlGaAs, and thickness is between 10～30 nm.
Ga 0.5In 0.5P top battery 500 specifically is comprised of AlGaInP back surface field layer, p-GaInP base, n-GaInP emitter region, AlInP Window layer.
The preparation method of aforementioned multijunction solar cell mainly comprises the following steps:
At first, the monocrystalline Ge substrate of selecting the P type to mix is as the base of battery at the bottom of the Ge.Enter the MOCVD growth, lead in advance PH at the germanium substrate 3, phosphorus atoms being diffused into obtaining the N-type emitter region in the germanium substrate, its thickness is about 100nm, and doping content is 1 * 10 19Cm -3Epitaxial growth N-shaped GaInP Window layer 110 again, thickness 10～50nm, and to overcome the reverse farmland that extension produces on the germanium substrate, its lattice constant and Ge mate, and doping content is about 1 * 10 17Cm -3
Next step, growing n-type In 0.01Ga 0.99As resilient coating 200, the thickness of resilient coating is 1000nm, doping content is about 1 * 10 18Cm -3
Next step, the tunnel junctions 300 of end battery in the growth, tunnel junctions by the N-shaped doping content greater than 1 * 10 19Cm -3, thickness is about the GaAs layer of 20nm and p-type is mixed greater than 5 * 10 19Cm -3, the thickness GaAs layer that is about 20nm forms.‘
Next step, battery in tunnel junctions 300 forms.Comprise the following steps: specifically that at first the about 50nm of growth thickness, P type doping content are about 1 * 10 18Cm -3The AlGaAs layer, as the back surface field layer 310 of middle battery.Then, the In of epitaxial growth P type doping 0.01Ga 0.99Battery base in the As conduct, doping content is 1 * 10 16Cm -3～2 * 10 18Cm -3Between gradient doping, thickness is 3000nm.At In 0.01Ga 0.99In grows on the As base 320 0.15Ga 0.85As stress modulation layer 330, wherein the growth rate of InGaAs is 0.1～10 nm/s, thickness is 50nm.Then, introduce growth interruption, the growth interruption time is 5～100 seconds.Then, epitaxial growth InAs quantum-dot structure 342, growth rate is 0.01～0.5 ML/s(monoatomic layer/second), thickness is 1.5～4 monoatomic layers.Concrete technology: at In 0.15Ga 0.85As stress modulation layer 330 surface deposition 2.0ML(monolayer) thus InAs obtain the InAs quantum-dot structure; Then introduce growth interruption, the growth interruption time is 5～100 seconds; Then at InAs quantum dot surface coverage 10nm In 0.15Ga 0.85As is as cap rock 341, repeated growth InAs quantum dot 342 and In 0.15Ga 0.85As cap rock 341 repeats 20 times, has just obtained the lamination quantum-dot structure 340 that is comprised of InAs quantum dot and InGaAs cap rock.At last, growth thickness is 100nm on InAs lamination quantum dot molecular structure 340, and doping content is 1 * 10 18Cm -3To 1 * 10 19Cm -3Between n-In 0.01Ga 0.99Battery emitter region 350 in the As conduct.Growth thickness is the N-shaped Al of 20nm on emitter region 350 0.5In 0.5The P layer, as the Window layer 360 of middle battery, its doping content is about 5 * 10 18Cm -3
Next step, the tunnel junctions 400 of battery in middle battery Window layer 360 growth tops.Tunnel junctions 400 comprises that the N-shaped doping content is greater than 1 * 10 19Cm -3, thickness is that the GaAs layer of 20nm and p-type are mixed greater than 5 * 10 19Cm -3, thickness is the Al of 15nm 0.3Ga 0.3The As layer.
Next step forms top battery 500 in tunnel junctions 400.Concrete technology: at first, on tunnel junctions 400 growth thickness be 50nm, p-type AlGaInP layer as the back surface field layer of top battery, AlGaInP back surface field layer crystal lattice constant and Ge coupling, the p-type doping content is about 5 * 10 17Cm -3Then growth thickness is that 1000nm, p-type doping content are 1 * 10 17Cm -3～1 * 10 18Cm -3Ga 0.5In 0.5The P layer is as battery base, top; Then growth thickness 70nm, p-type doping content are about 6 * 10 18Cm -3Ga 0.5In 0.5The P layer is as battery emitter region, top, thus acquisition top battery; At last, growth thickness is the N-shaped Al of 20～100nm 0.5In 0.5The P layer is as the Window layer of top battery.
Next step, the about 500nm of growth thickness, N-shaped doping content are about 5 * 10 18Cm -3GaAs block layer 600 as ohmic contact layer.
Clearly, explanation of the present invention should not be construed as and is limited only within above-described embodiment, but comprises the whole execution modes that utilize the present invention to conceive.

Claims (10)

1. three-joint solar cell comprises end battery, middle battery and top battery, it is characterized in that: described middle battery comprises: In xGa 1-xAs stress modulation layer, and by InAs quantum dot and In xGa 1-xThe lamination InAs quantum-dot structure that the As cap rock forms, described In xGa 1-xAs stress modulation layer is the In component greater than 0.01 InGaAs layer, and thickness is lower than its critical thickness; Described lamination InAs quantum-dot structure is formed at In xGa 1-xOn the As stress modulation layer.
2. three-joint solar cell according to claim 1 is characterized in that: described In xGa 1-xIn in the As stress modulation layer xGa 1-xThe In component x of As layer is 0.1～0.6.
3. three-joint solar cell according to claim 1 is characterized in that: described In xGa 1-xThe thickness of As stress modulation layer is 10-100nm, is lower than the critical thickness of corresponding InGaAs material.
4. three-joint solar cell according to claim 1 is characterized in that: described In xGa 1-xAs stress modulation layer surface formed the height relief fabric.
5. three-joint solar cell according to claim 1 is characterized in that: In in the described lamination InAs quantum-dot structure xGa 1-xThe In component x of As cap rock is 0.05-0.5.
6. the manufacture method of three-joint solar cell, it comprises the step that forms end battery, middle battery and top battery, wherein said middle battery comprises following step by lower mask body:
Epitaxial growth In xGa 1-xAs stress modulation layer, the In component is greater than 0.01 InGaAs layer, and thickness is lower than its critical thickness;
Form lamination InAs quantum dot knot at described stress modulation layer, it is by InAs quantum dot and In xGa 1-xThe As cap rock forms.
7. three-joint solar cell according to claim 5 is characterized in that: at the described In of epitaxial growth xGa 1-xBehind the As stress modulation layer, introduce growth interruption to strengthen atomic migration, the growth interruption time is 5～100 seconds.
8. three-joint solar cell according to claim 1 is characterized in that: In in the described lamination InAs quantum-dot structure xGa 1-xThe growth rate of As cap rock is 0.1～5nm/s, and thickness is 5～50nm.
9. three-joint solar cell according to claim 1, it is characterized in that: the growth rate of InAs quantum dot layer is 0.01～5 ML/s in the described lamination InAs quantum-dot structure, thickness is 1.5～4 monoatomic layers.
10. three-joint solar cell according to claim 1 is characterized in that: behind the described InAs quantum dot layer of epitaxial growth, introduce growth interruption to strengthen atomic migration, the growth interruption time is 5～100 seconds.
CN201210406609XA 2012-10-23 2012-10-23 Triple-junction solar cell and preparation method thereof Pending CN102931271A (en)

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Application publication date: 20130213