CN101901854A - Method for preparing InGaP/GaAs/InGaAs three-junction thin film solar cell - Google Patents
Method for preparing InGaP/GaAs/InGaAs three-junction thin film solar cell Download PDFInfo
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Abstract
The invention provides a method for preparing an InGaP/GaAs/InGaAs three-junction thin film solar cell. The method comprises the following steps of: epitaxially growing a top InGaP sub-cell and a middle GaAs sub-cell on a Ge or GaAs substrate; growing an InGaP or InGaAs stress transition layer with gradient In component; forming a bottom InGaAs sub-cell with complete stress relaxation on the stress transition layer; adhering the InGaAs sub-cell to a light substrate with heat dissipation; etching off a sacrificial layer by using hydrofluoric acid; and naturally stripping off the Ge or GaAs substrate to obtain the InGaP/GaAs/InGaAs three-junction thin film solar cell. In the method, the expensive Ge or GaAs substrate which is sacrificed during the preparation of the conventional device is replaced by a new substrate with low cost, low density and high heat dissipation, the Ge or GaAs substrate is recycled, and the production cost of the solar cell is greatly reduced.
Description
Technical field
The invention belongs to the epitaxial growth and the device preparation field of compound semiconductor thin film solar cell, be specifically related to growth InGaP/GaAs/InGaAs three knot high performance solar batteries materials on Ge or GaAs substrate, and then on the good new substrate of low price, low-density, thermal diffusivity, prepare InGaP/GaAs/InGaAs three knot efficient thin-film solar cell devices, realize the method that Ge or GaAs substrate can be repeatedly used simultaneously.
Background technology
Because the ecological deterioration of petering out and constantly causing of non-renewable energy resources such as coal, oil, the mankind press for and use green energy resource to solve the huge problem that is faced as people.Utilize the solar cell of photoelectric conversion technique manufacturing solar energy directly can be converted to electric energy, this has reduced the dependence of people's productive life to coal, petroleum and natural gas to a great extent, becomes one of effective means of utilizing green energy resource.The Ⅲ-ⅤZu Huahewubandaoti multijunction solar cell is the highest a kind of solar cell of conversion efficiency, have advantages such as resistance to elevated temperatures, capability of resistance to radiation are strong, good temp characteristic simultaneously, become mainstream technology already the insensitive space of price photo-voltaic power supply.In the last few years, along with the development of condensation photovoltaic technology, GaAs and related compound III-V II-VI group solar cell more and more received publicity because of its high-photoelectric transformation efficiency.The condensation photovoltaic technology is by carrying out a bigger sunlight of area high magnification optically focused, shine after concentrating on the smaller solar-energy photo-voltaic cell of area and generate electricity, thereby saves solar cell wafer on a large scale.This device utilizes large tracts of land, cheap beam condensing unit to replace expensive and battery chip in short supply, and then reaches the purpose that reduces the solar energy power generating cost significantly, makes solar energy power generating have the ability of competing with conventional energy resource.Therefore the condensation photovoltaic technology based on the Ⅲ-ⅤZu Huahewubandaoti multijunction solar cell has become the photovoltaic technology that market prospects are arranged very much.
To those skilled in the art, the InGaP/GaAs/Ge three-joint solar cell be the most ripe at present also be Ⅲ-ⅤZu Huahewubandaoti multijunction solar cell the most efficiently, the lattice constant of each sub-battery of the type solar cell is mated substantially, and band gap width is respectively from top to down: InGaP is～1.86eV, GaAs is～1.42eV, Ge is～0.78eV, can more effectively utilize solar spectrum, its conversion efficiency (AM1.5) is up to 32% (U.S. spectrographic laboratory), and under the optically focused condition, its efficient is 40.1%.Yet there is two large problems in InGaP/GaAs/Ge three junction batteries.First problem is that this battery is that it can not realize the optimum utilization of solar spectrum in the three ligament crack combining structures that guarantee to realize a kind of compromise consideration under the lattice Perfect Matchings condition.Wherein, the photogenerated current that Ge battery is produced is that not matching of current density will be to the conversion efficiency generation influence to a certain degree of multijunction solar cell between the sub-battery that this caused about the twice of InGaP and the sub-battery of GaAs.The another one problem is that the resource of Ge is more rare on the earth, and very expensive.The cost of Ge substrate accounts for 30～50% of InGaP/GaAs/Ge solar cell total cost, is to cause one of expensive principal element of multijunction cell.When large-scale production, the problem that the Ge substrate is rare and expensive will further highlight.At present, whole world high-efficiency solar will concentrate on Belgian grace with the living factory owner of germanium wafer can (Umicore) company and U.S. crystal technology group (AXT), and the strategic demand of China's autonomous epitaxial growth Ⅲ-ⅤZu Huahewubandaoti multijunction solar cell has been arrived in this serious threat.Therefore how improving the conversion efficiency of Ⅲ-ⅤZu Huahewubandaoti multijunction solar cell effectively and further reduce the cell preparation cost is whether this technology can finally move towards one of key of scale terrestrial power generation.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of InGaP/GaAs/InGaAs three-junction thin film solar cell, have the low low price of cost, low-density, advantage that thermal diffusivity is good, and realize that Ge or GaAs substrate can be repeatedly used.
1, a kind of preparation method of InGaP/GaAs/InGaAs three-junction thin film solar cell is specially:
(1) epitaxial growth Al on Ge or GaAs substrate
xGa
1-xAs is as sacrifice layer, 0.4＜x≤1;
(2) epitaxial growth forms the sub-battery of bottom InGaP on sacrifice layer;
(3) epitaxial growth forms the sub-battery of middle part GaAs on the sub-battery of bottom InGaP;
(4) InGaP of epitaxial growth In content gradually variational or InGaAs transition of stress layer on the sub-battery of middle part GaAs, the contact interface of this transition of stress layer and the sub-battery of middle part GaAs meets the lattice match requirement;
(5) the sub-battery of top InGaAs of the complete relaxation of epitaxial growth formation stress on InGaP or InGaAs transition of stress layer, the contact interface of sub-battery of top InGaAs and InGaP or InGaAs transition of stress layer meets the lattice match requirement;
(6) form Ohmic electrode on the surface of the sub-battery of top InGaAs;
(7) the sub-battery of InGaAs is bonded on the lightweight substrate with thermal diffusivity;
(8) adopt hydrofluoric acid to erode sacrifice layer, Ge or GaAs substrate are peeled off naturally and are obtained the InGaP/GaAs/InGaAs three-junction thin film solar cell.
Technique effect of the present invention is embodied in: on the one hand, the GaInP/GaAs/InGaAs three-joint solar cell has had the higher conversion efficiency more than 40%.By improving growth technique, reduce the dislocation density of sub-battery material, still might in present existing GaInP/GaAs/InGaAs three-joint solar cell, continue to insert the sub-battery of more knots, realize higher conversion efficiency with this; On the other hand, the encapsulation of the later stage of GaInP/GaAs/InGaAs three-joint solar cell is by at first adopting the extension lift-off technology to realize.By growth GaInP/GaAs/InGaAs three-joint solar cell, and adopt the extension lift-off technology, substrate can repeatedly be utilized, reduce production costs thereby can effectively separate substrate and battery active region.Simultaneously, the battery active region of separating can be by being bonded on the good base material of thermal diffusivity (as Si, copper sheet etc.), and the battery heat dissipation problem will greatly be improved; If it is bonded on the cheap base material (as glass etc.), the battery price will further reduce; Moreover, if use the less base material (as Si) of density, can alleviate the weight of entire cell, the space flight and aviation that helps multijunction solar cell is used.
Description of drawings
Fig. 1 is the Ga on the lightweight substrate (as sheet copper or Si or glass) that is bonded at thermal diffusivity of the present invention
0.5In
0.5P/GaAs/Ga
0.7In
0.3The side sectional view of As three knot efficient thin-film solar cell devices.
Fig. 2 is the side sectional view of AlGaAs sacrifice layer of high Al component (＞0.4) of having grown on Ge or GaAs substrate.
Fig. 3 has formed bottom Ga on the AlGaAs of high Al component sacrifice layer
0.5In
0.5Side sectional view behind the sub-battery of P.
Fig. 4 is at bottom Ga
0.5In
0.5Side sectional view in the middle part of epitaxial growth forms on the sub-battery of P behind the sub-battery of GaAs.
Fig. 5 is the side sectional view after epitaxial growth forms on the sub-battery of middle part GaAs.
Fig. 6 has formed Ga on Ge or GaAs substrate
0.5In
0.5P/GaAs/Ga
0.7In
0.3The side sectional view of As three knot high efficiency solar cells.
Fig. 7 is the Ga at Ge or GaAs substrate
0.5In
0.5P/GaAs/Ga
0.7In
0.3Formed the side sectional view behind the AuGeNi/Au electrode on the As three knot high efficiency solar cell upper surfaces.
Fig. 8 is at Ga
0.5In
0.5P/GaAs/Ga
0.7In
0.3Bonding side sectional view behind the lightweight substrate of one deck thermal diffusivity (as sheet copper, Si or glass) on the As three knot high efficiency solar cell upper surface AuGeNi/Au electrodes.
Fig. 9 is Ge or GaAs substrate and the bonded Ga of the lightweight substrate of thermal diffusivity (as sheet copper, Si or glass)
0.5In
0.5P/GaAs/Ga
0.7In
0.3Side sectional view after As three knot high efficiency solar cells are separated.
Embodiment
Describe the present invention in detail below with reference to drawings and Examples.
Embodiment one:
1) (001) face Ge substrate 1 is cleaned up, and the MOCVD reative cell of packing into, at first toasted 10 minutes down at 750 ℃.Then, be cooled to 600 ℃, epitaxial growth Al component is 0.45 Al
0.45Ga
0.55As sacrifice layer 2 (as shown in Figure 2).
2) at Al
0.45Ga
0.55Form top Ga on the As sacrifice layer 2
0.5In
0.5The sub-battery of P (as shown in Figure 3).The growing n-type GaAs of elder generation contact layer 3, AlInP Window layer 4, regrowth n type Ga
0.5In
0.5 P emission layer 5, growing p-type Ga then
0.5In
0.5 A P base 6 and a p type GaInP back of the body layer 7, last growing p-type AlInP base 8.
3) at bottom Ga
0.5In
0.5Epitaxial growth forms the middle part sub-battery of GaAs (as shown in Figure 4) on the sub-battery of P.First growth AlGaAs Window layer 9, regrowth n type GaAs emission layer 10, growing p-type GaAs base 11 then, the AlGaAs that grows an at last back of the body layer 12.
4) In of epitaxial growth In content gradually variational on the sub-battery of middle part GaAs
xGa
1-xP transition of stress layer 13 (as shown in Figure 5).In the MOCVD epitaxial process, by the flow-rate ratio in conditioned reaction source, In
xGa
1-xIn content among the P little by little brings up to 76% from 50%, scheming slowly to discharge stress, and misfit dislocation is confined in this transition zone.In
xGa
1-xIn content among the P be changed to continuous linear change, rate of change is 13%/μ m.
5) at In
xGa
1-xEpitaxial growth forms top Ga on the P transition of stress layer 13
0.7In
0.3As battery has formed Ga afterwards
0.5In
0.5P/GaAs/Ga
0.7In
0.3As three knot high efficiency solar cells (as shown in Figure 6).The growth GaInP of elder generation Window layer 14, regrowth n type Ga
0.7In
0.3As emission layer 15, growing p-type Ga then
0.7In
0.3As base 16, the GaInP that grows an at last back of the body layer 17.The top Ga of growth this moment
0.7In
0.3The dislocation density that As battery is had is 5 * 10
6Cm
-2, surface roughness is 5nm.
6) at Ga
0.5In
0.5P/GaAs/Ga
0.7In
0.3Formed AuGeNi/Au electrode 18 (as shown in Figure 7) on the As three knot high efficiency solar cell upper surfaces.By electron beam evaporation process, evaporation AuGeNi/Au electrode 18, and under nitrogen environment, anneal 3 minutes to form ohmic contact for 450 ℃.
7) at Ga
0.5In
0.5P/GaAs/Ga
0.7In
0.3 Join sheet copper 19 surfaces (as shown in Figure 8) to by polyimide adhesive on the As three knot high efficiency solar cell upper surface AuGeNi/Au electrodes 18, upper surface AuGeNi/Au electrode 18 links to each other with sheet copper 19.
8) hydrofluoric acid of use 10% falls Al as corrosive liquid by selective corrosion
0.45Ga
0.55Behind the As sacrifice layer 2, Ge substrate 1 and the bonded Ga of sheet copper 19
0.5In
0.5P/GaAs/Ga
0.7In
0.3As three knot high efficiency solar cells are separated, and have stayed above-mentioned two thin layers (as shown in Figure 9) simultaneously.This moment, the Ge substrate was intactly kept, used deionized water that the Ge substrate surface is cleaned, and dried up substrate surface with nitrogen gun again, and the Ge substrate can be used once more.
When using battery of the present invention, can make post-production to it as follows: at the bonding Ga of sheet copper
0.5In
0.5P/GaAs/Ga
0.7In
0.3On the n type GaAs contact layer 3 of the another side of As three knot high efficiency solar cells, evaporation Ti/Au electrode 20, and on AlInP Window layer 4, deposited double-deck antireflective film 21 (as shown in Figure 1).Through the surface of traditional handicrafts such as photoetching, electrode evaporation, alloying, electrode thicken at battery, promptly not on the one side of bonding copper coin,, form Ti/Au electrode 20 by electron beam evaporation process evaporation Ti, Au successively, under nitrogen environment, anneal 3 minutes to form ohmic contact for 450 ℃.Etch away Ti/Au electrode 20 belows ohmic contact layer 3 in addition by selectivity ICP lithographic method then, make it to occur the platform of an AlInP Window layer 4, and then on the platform of AlInP Window layer 4, prepare double-deck antireflective film 21 by the method for hot evaporation, finally prepared the Ga that is bonded on the sheet copper
0.5In
0.5P/GaAs/Ga
0.7In
0.3As three knot efficient thin-film solar cell devices (as shown in Figure 1).
Embodiment two:
Used substrate is (001) face GaAs substrate in the present embodiment, and the notch cuttype that is changed to of In content changes in the InGaP transition of stress layer 13, and rate of change is 13%/μ m, and per 0.25 μ m is a ladder.The top Ga of growth this moment
0.7In
0.3The dislocation density that As battery is had is 2 * 10
6Cm
-2, surface roughness is 2nm.
Embodiment three:
1) (001) face GaAs substrate 1 is cleaned up, and the MOCVD reative cell of packing into, at first toasted 10 minutes down at 750 ℃.Then, be cooled to 650 ℃, epitaxial growth Al component is 0.8 Al
0.8Ga
0.2As sacrifice layer 2 (as shown in Figure 2).
2) at Al
0.8Ga
0.2Form top Ga on the As sacrifice layer 2
0.5In
0.5The sub-battery of P (as shown in Figure 3).The growing n-type GaAs of elder generation contact layer 3, AlInP Window layer 4, regrowth n type Ga
0.5In
0.5 P emission layer 5, the p type Ga that grows low-doped then
0.5In
0.5 A P base 6 and a p type GaInP back of the body layer 7, last growing p-type AlInP base 8.
3) at bottom Ga
0.5In
0.5Epitaxial growth forms the middle part sub-battery of GaAs (as shown in Figure 4) on the sub-battery of P.First growth AlGaAs Window layer 9, regrowth n type GaAs emission layer 10, growing p-type GaAs base 11 then, the AlGaAs that grows an at last back of the body layer 12.
4) In of epitaxial growth In content gradually variational on the sub-battery of middle part GaAs
xGa
1-xAs transition of stress layer 13 (as shown in Figure 5).In the MOCVD epitaxial process, by the flow-rate ratio in conditioned reaction source, In
xGa
1-xIn content among the As little by little brings up to 30% from 0, scheming slowly to discharge stress, and misfit dislocation is confined in this transition zone.In
xGa
1-xIn content among the As be changed to continuous linear change, rate of change is 10%/μ m.
5) at In
xGa
1-xEpitaxial growth forms top Ga on the As transition of stress layer 13
0.7In
0.3As battery has formed Ga afterwards
0.5In
0.5P/GaAs/Ga
0.7In
0.3As three knot high efficiency solar cells (as shown in Figure 6).The growth GaInP of elder generation Window layer 14, regrowth n type Ga
0.7In
0.3As emission layer 15, growing p-type Ga then
0.7In
0.3As base 16, the GaInP that grows an at last back of the body layer 17.The top Ga of growth this moment
0.7In
0.3The dislocation density that As battery is had is 3 * 10
6Cm
-2, surface roughness is 3nm.
6) at Ga
0.5In
0.5P/GaAs/Ga
0.7In
0.3Formed AuGeNi/Au electrode 18 (as shown in Figure 7) on the As three knot high efficiency solar cell upper surfaces.By electron beam evaporation process, evaporation AuGeNi/Au electrode 18, and under nitrogen environment, anneal 3 minutes to form ohmic contact for 450 ℃.
7) at Ga
0.5In
0.5P/GaAs/Ga
0.7In
0.3Join thin Si plate 19 surfaces (as shown in Figure 8) to by polyimide adhesive on the As three knot high efficiency solar cell upper surface AuGeNi/Au electrodes 18, upper surface AuGeNi/Au electrode 18 links to each other with thin Si plate 19.
8) hydrofluoric acid of use 20% falls Al as corrosive liquid by selective corrosion
0.8Ga
0.2Behind the As sacrifice layer 2, Ge substrate 1 and the bonded Ga of thin Si plate 19
0.5In
0.5P/GaAs/Ga
0.7In
0.3As three knot high efficiency solar cells are separated, and have stayed above-mentioned two thin layers (as shown in Figure 9) simultaneously.This moment, the Ge substrate was intactly kept, used deionized water that the Ge substrate surface is cleaned, and dried up substrate surface with nitrogen gun again, and the Ge substrate can be used once more.
Embodiment four:
1) (001) face GaAs substrate 1 is cleaned up, and the MOCVD reative cell of packing into, at first toasted 10 minutes down at 750 ℃.Then, be cooled to 650 ℃, epitaxial growth Al component is 1 AlAs sacrifice layer 2 (as shown in Figure 2).
2) on AlAs sacrifice layer 2, form top Ga
0.5In
0.5The sub-battery of P (as shown in Figure 3).The growing n-type GaAs of elder generation contact layer 3, AlInP Window layer 4, regrowth n type Ga
0.5In
0.5 P emission layer 5, the p type Ga that grows low-doped then
0.5In
0.5 A P base 6 and a p type GaInP back of the body layer 7, last growing p-type AlInP base 8.
3) at bottom Ga
0.5In
0.5Epitaxial growth forms the middle part sub-battery of GaAs (as shown in Figure 4) on the sub-battery of P.First growth AlGaAs Window layer 9, regrowth n type GaAs emission layer 10, growing p-type GaAs base 11 then, the AlGaAs that grows an at last back of the body layer 12.
4) In of epitaxial growth In content gradually variational on the sub-battery of middle part GaAs
xGa
1-xAs transition of stress layer 13 (as shown in Figure 5).In the MOCVD epitaxial process, by the flow-rate ratio in conditioned reaction source, In
xGa
1-xIn content among the As little by little brings up to 30% from 0, scheming slowly to discharge stress, and misfit dislocation is confined in this transition zone.In
xGa
1-xThe notch cuttype that is changed to of the In content among the As changes, and rate of change is 10%/μ m, and per 0.25 μ m is a ladder.
5) at In
xGa
1-xEpitaxial growth forms top Ga on the As transition of stress layer 13
0.7In
0.3As battery has formed Ga afterwards
0.5In
0.5P/GaAs/Ga
0.7In
0.3As three knot high efficiency solar cells (as shown in Figure 6).The growth GaInP of elder generation Window layer 14, regrowth n type Ga
0.7In
0.3As emission layer 15, growing p-type Ga then
0.7In
0.3As base 16, the GaInP that grows an at last back of the body layer 17.The top Ga of growth this moment
0.7In
0.3The dislocation density that As battery is had is 1 * 10
6Cm
-2, surface roughness is 1nm.
6) at Ga
0.5In
0.5P/GaAs/Ga
0.7In
0.3Formed AuGeNi/Au electrode 18 (as shown in Figure 7) on the As three knot high efficiency solar cell upper surfaces.By electron beam evaporation process, evaporation AuGeNi/Au electrode 18, and under nitrogen environment, anneal 3 minutes to form ohmic contact for 450 ℃.
7) at Ga
0.5In
0.5P/GaAs/Ga
0.7In
0.3Join thin glass plate 19 surfaces (as shown in Figure 8) to by polyimide adhesive on the As three knot high efficiency solar cell upper surface AuGeNi/Au electrodes 18, upper surface AuGeNi/Au electrode 18 links to each other with thin glass plate 19.
8) use 20% hydrofluoric acid as corrosive liquid, fall AlAs sacrifice layer 2 by selective corrosion after, Ge substrate 1 and the bonded Ga of thin glass plate 19
0.5In
0.5P/GaAs/Ga
0.7In
0.3As three knot high efficiency solar cells are separated, and have stayed above-mentioned two thin layers (as shown in Figure 9) simultaneously.This moment, the Ge substrate was intactly kept, used deionized water that the Ge substrate surface is cleaned, and dried up substrate surface with nitrogen gun again, and the Ge substrate can be used once more.
Claims (3)
1. the preparation method of an InGaP/GaAs/InGaAs three-junction thin film solar cell is specially:
(1) epitaxial growth Al on Ge or GaAs substrate
xGa
1-xAs is as sacrifice layer, 0.4＜x≤1;
(2) epitaxial growth forms the sub-battery of bottom InGaP on sacrifice layer;
(3) epitaxial growth forms the sub-battery of middle part GaAs on the sub-battery of bottom InGaP;
(4) InGaP of epitaxial growth In content gradually variational or InGaAs transition of stress layer on the sub-battery of middle part GaAs, the contact interface of this transition of stress layer and the sub-battery of middle part GaAs meets the lattice match requirement;
(5) the sub-battery of top InGaAs of the complete relaxation of epitaxial growth formation stress on InGaP or InGaAs transition of stress layer, the contact interface of sub-battery of top InGaAs and InGaP or InGaAs transition of stress layer meets the lattice match requirement;
(6) form Ohmic electrode on the surface of the sub-battery of top InGaAs;
(7) the sub-battery of InGaAs is bonded on the lightweight substrate with thermal diffusivity;
(8) adopt hydrofluoric acid to erode sacrifice layer, Ge or GaAs substrate are peeled off naturally and are obtained the InGaP/GaAs/InGaAs three-junction thin film solar cell.
2. the manufacture method of InGaP/GaAs/InGaAs three-junction thin film solar cell as claimed in claim 1 is characterized in that, the In molar content of described InGaP from 50% bring up to 76% or the In molar content of InGaAs bring up to 30% from 0.
3. the manufacture method of InGaP/GaAs/InGaAs three-junction thin film solar cell as claimed in claim 1 is characterized in that, described substrate is Si or copper sheet or glass.
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