CN104916715B - A kind of preparation method of quantum dot five-junction solar cell - Google Patents
A kind of preparation method of quantum dot five-junction solar cell Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 28
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- 239000011248 coating agent Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
The present invention relates to area of solar cell, a kind of preparation method of quantum dot five-junction solar cell is essentially disclosed.The battery prepares the joint solar cells of InP two using the forward direction growth of MOCVD technologies extension and extension back growth prepares GaAs three-joint solar cells, it is quantum dot five-junction solar cell to be bonded the joint solar cells of InP two and GaAs three-joint solar cells by directly bonding semiconductor technique, and the structure for preparing gained battery is followed successively by GaAs cap layers, the first knot AlxGa1‑xIn0.5P batteries, the first tunnel junctions, the second knot AlxGa1‑xAs batteries, the second tunnel junctions, the 3rd knot GaAs batteries, the 3rd tunnel junctions, bond contact layer, the 4th knot InxGa1‑ xAsyP1‑yBattery, the 4th tunnel junctions, the 5th knot InxGa1‑xAs batteries, InP cushions and InP substrate.The beneficial effects of the invention are as follows：It this method reduce the probability of happening of the waste of raw materials phenomenon caused by epitaxial growth operational error in cell manufacturing process；In addition, directly bonding semiconductor technological operation is simple and easy to apply in the preparation method of the battery, the efficiency of battery production is improved.
Description
Technical field
The present invention relates to area of solar cell, more particularly, to a kind of preparation side of quantum dot five-junction solar cell
Method.
Background technology
At present, because the excessive abuse of traditional energy has had resulted in serious destruction to ecological environment, and the ring of people
Protect consciousness also more and more stronger.At the same time, people are accomplished by seeking the new energy that more cleans to replace traditional energy, to drop
The pollution level of tail gas produced by low traditional energy to air etc..
Because solar energy is a kind of inexhaustible clean energy resource, so the development to photovoltaic industry is given now
Great attention is given.This just needs the manufacture for carrying out solar cell, industrializes it.Industrialized production needs to consider production cost
The problems such as.Especially for the solar radiant energy for more fully utilizing each wavelength band, so needing to design a set of production
The method of many knot tandem solar cells.Traditional preparation method is to use MOCVD (Metal-organic Chemical
Vapor Deposition) carry out each functional layer filming process in tandem solar cell.If however, cascade solar-electricity
The knot number of contained single battery is more in pond, will increase per the defect between joint solar cell linkage interface, so as to influence
The transmission of electronics and hole in tandem solar cell.
As can be seen here, a kind of preparation method of multijunction solar cell how is worked out, unijunction solar electricity can be reduced
Defects count between the linkage interface of pond, is current those skilled in the art's urgent problem to be solved.
The content of the invention
In order to solve the above problems, lack between can reducing unijunction solar cell linkage interface the invention provides one kind
Fall into quantum dot five-junction solar cell of quantity and preparation method thereof.
The present invention relates to a kind of method for preparing the quantum dot five-junction solar cell, mainly include the following steps that：
(a) the positive joint solar cell of grown InP two of MOCVD epitaxy is passed through；
(b) MOCVD epitaxy back growth GaAs three-joint solar cells are passed through；
(c) joint solar cells of InP two and the knot sun of the GaAs tri- are realized by directly bonding semiconductor technique
The bonding of energy battery；
(d) stripping of sacrifice layer is completed by selective corrosion technique, the quantum dot five-junction solar cell is obtained.
The joint solar cells of InP two described in step (a), successively the extension forward direction growth thickness 0.1-0.3 in InP substrate
μm InP cushions, the 5th knot InxGa1-xAs batteries, the 4th tunnel junctions, the 4th knot InxGa1-xAsyP1-yBattery and thickness 100-
1000nm InP bond contacts layer, wherein 0.3≤x≤0.8,0.3≤y≤0.7.
GaAs three-joint solar cells described in step (b), successively extension back growth thickness on gaas substrates
0.1-0.3 μm of GaAs cushions, the GaInP corrosion barrier layers of 0.1-0.3 μm of thickness, thickness 100-500nm n-type doping
GaAs cap layers, the first knot AlxGa1-xIn0.5P batteries, the first tunnel junctions, the second knot AlxGa1-xAs batteries, the second tunnel junctions, thickness
The Window layer of 30-200nm the 3rd knot GaAs batteries, emission layer, the thickness 20- of thickness 50-200nm the 3rd knot GaAs batteries
100nm quantum dot soakage layer, quantum dot composite bed, the base layer of thickness 2000-4000nm the 3rd knot GaAs batteries, the 3rd
The GaAs bond contacts layer of tunnel junctions, thickness 100-1000nm, wherein 0.2≤x≤0.5.
The sacrifice layer is the GaAs substrates, the GaAs cushions and the GaInP corrosion barrier layers, the quantum
Point soakage layer is that have regular and equally distributed figure with prepared by nano impression graphical method.
Further, comprise the following steps in step (c)：
The bonding type protected full of nitrogen is placed in after InP bond contacts layer is fitted with GaAs bond contacts layer
Intracavitary is bonded, and completes the bonding of the joint solar cells of InP two and the GaAs three-joint solar cells.
Further, comprise the following steps in step (d)：
Using GaAs substrates described in corrosion, the GaAs cushions and the GaInP corrosion barrier layers is corroded, institute is completed
State the stripping of sacrifice layer.
Further, the 5th knot In in step (a)xGa1-xAs batteries, the 4th tunnel junctions, the 4th knot
InxGa1-xAsyP1-yBattery includes following growth course respectively：
The 5th knot InxGa1-xAs batteries：Thickness 50-400nm p-type doping InP back surface field layers, thickness are grown to successively
2000-5000nm p-type doping InxGa1-xThe n-type doping In of As bases, thickness 50-400nmxGa1-xAs launch sites and thickness
30-200nm n-type doping InP Window layers；4th tunnel junctions：Be grown to successively thickness 10-100nm n-type layer of InP and
Thickness 10-100nm p-type layer of InP；The 4th knot InxGa1-xAsyP1-yBattery：Thickness 30-300nm p-type is grown to successively
Adulterate InP back surface field layers, thickness 2000-5000nm p-type doping InxGa1-xAsyP1-yThe n-type doping of base, thickness 50-400nm
InxGa1-xAsyP1-yLaunch site and thickness 30-200nm n-type doping InP Window layers；Wherein, 0.3≤x≤0.8,0.3≤y≤
0.7。
Further, the first knot Al described in step (b)xGa1-xIn0.5P batteries, first tunnel junctions, described second
Tie AlxGa1-xAs batteries, second tunnel junctions, the quantum dot composite bed and the 3rd tunnel junctions include following grew
Journey：
The first knot AlxGa1-xIn0.5P batteries：Thickness 30-200nm p-type doping Al is grown to successivelyxGa1-xIn0.5P
Back surface field layer, thickness 500-2000nm p-type doping AlxGa1-xIn0.5The n-type doping Al of P bases, thickness 50-200nmxGa1- xIn0.5P launch sites and thickness 30-200nm n-type doping AlxGa1-xIn0.5P Window layers；First tunnel junctions：Grow successively
For thickness 10-100nm n-type AlxGa1-xIn0.5The Al of P layers and thickness 10-100nm of p-typexGa1-xAs layers；Second knot
AlxGa1-xAs batteries：Thickness 30-200nm p-type doping Al is grown to successivelyxGa1-xIn0.5P back surface field layers, thickness 1000-
3000nm p-type doping AlxGa1-xThe n-type doping Al of As bases, thickness 50-200nmxGa1-xAs launch sites and thickness 30-
200nm n-type doping AlInP Window layers；Second tunnel junctions：Be grown to successively thickness 10-100nm GaInP layers of n-type and
Thickness 10-100nm p-type AlxGa1-xAs layers；The quantum dot composite bed：Quantum dot layer is grown to successively and for compensation rate
The coating of son point stress；3rd tunnel junctions：Thickness 10-100nm n-type In is grown to successivelyxGa1-xAs layers and thickness
10-100nm p-type AlyGa1-yAs layers.
The first knot AlxGa1-xIn0.5P batteries, first tunnel junctions, the second knot AlxGa1-xIt is As batteries, described
0.2≤x≤0.5 in second tunnel junctions.
0≤x≤0.1,0≤y≤0.5 in 3rd tunnel junctions.
Further, the quantum dot soakage layer is GaAs layers or InxGa1-xAs layers；The quantum dot composite bed is outer successively
Epitaxial growth quantum dot and coating, the quantum dot are InAs or InxGa1-xAs quantum dots, wherein 0≤x≤0.1.
Present invention additionally comprises a kind of preparation method of quantum dot five-junction solar cell, wherein being carried out to quantum dot soakage layer
Nano impression figure, the nano impression graphical method is implemented in thousand grades of ultra-clean chambers, specifically includes following steps：
S1：Glue：Methyl phenyl ethers anisole is dissolved in by PMMA (Polymethylmethacrylate) particle and prepares impressing glue；
S2：Film：Glue is imprinted described in spin coating on the quantum dot soakage layer, impressing glue film is prepared；
S3：Impressing：Sample obtained by step S2 is placed in impressing mould, it is thin to the impressing glue by the impressing mould
Film carries out figure impressing；
S4：The demoulding：The impressing mould is opened after impressing and completes the demoulding；
S5：Remove cull：The impressing glue film sunk part is removed, until the quantum dot of the sunk part soaks
Profit layer, which is exposed, to be come；
S6：Plated film：Imprinted described in S5 on glue film and layer of sin is depositedxFilm；
S7：Peel off：To be imprinted described in S6 glue film and with directly contacted above the impressing glue film described in
SiNxFilm is peeled off in the lump；
S8：Etching：Gained sample in the S7 is performed etching, covered with the SiNxThe quantum dot soakage layer of film
Etching speed can obtain the quantum with regular figure after being less than the etching speed of exposed quantum dot soakage layer, etching
Point soakage layer.
A kind of preparation method of quantum dot five-junction solar cell of the present invention, compared with prior art with advantages below：
First, the method for preparing quantum dot five-junction solar cell is first extension back growth GaAs three-joint solars electricity
The positive joint solar cell of grown InP two of pond and extension, is linked together by bonding technology afterwards, due to by the quantum dot five
Joint solar cell is divided into two groups and prepared, it is to avoid because the epitaxial growth number of plies excessively occurs because of certain successively on the same substrate
One layer of not good waste for causing the battery to be unable to reach production standard, causing raw material of growth, improves the knot of quantum dot five too
The production efficiency of positive energy battery；Secondly, the preparation method is beneficial to the matching growth of lattice between every layer of the battery, can reduce this
The internal resistance of quantum dot five-junction solar cell.
Second, the quantum dot five-junction solar cell makes partly leading for extension back growth using directly bonding semiconductor technique
The joint solar cells of InP two bonding of body nano-quantum point GaAs three-joint solar cells and extension forward direction growth is integrated, should
The material of lattice severe mismatch can be directly connected to by technique, and it is very high to connect mechanical strength；In addition, the technique can
So that a large amount of dislocation and defect produced by lattice mismatch are limited in the coating region near bonded interface, it is to avoid to other
The performance of region material is impacted.
3rd, the quantum dot soakage layer in the quantum dot five-junction solar cell is using nano impression graphical method to quantum
The shape and size of point are accurately controlled, and are made the arrangement of quantum dot more regular, are easy to obtain consistent energy level, so that
Beneficial to satisfactory quantum dot Intermediate Gray is obtained, it is easy to produce electron-hole pair, finally photoelectric transformation efficiency is carried
It is high.
Brief description of the drawings
Fig. 1 is schematic flow sheet of the invention
Fig. 2 is the structural representation of the joint solar cells of InP two prepared by the present invention；
Fig. 3 is the structural representation of the GaAs three-joint solar cells prepared by the present invention；
Fig. 4 is that the structure after the joint solar cells of InP two and the bonding of GaAs three-joint solar cells is shown by the present invention
It is intended to；
Fig. 5 is the structural representation of the quantum dot five-junction solar cell prepared by the present invention；
Fig. 6 is the schematic diagram of nano impression graphical method in the present invention.
Label in figure is respectively：1-GaAs cap layers, the first knots of 2- AlxGa1-xIn0.5P batteries, the tunnel junctions of 3- first, 4-
Second knot AlxGa1-xAs batteries, the tunnel junctions of 5- second, the Window layer of the knot GaAs batteries of 6- the 3rd, the knot GaAs batteries of 7- the 3rd
Emission layer, 8- quantum dot soakage layers, 9- quantum dot composite beds, the base layer of the knot GaAs batteries of 10- the 3rd, the tunnel junctions of 11- the 3rd,
12-GaAs bond contacts layer, 13-InP bond contacts layer, the knot In of 14- the 4thxGa1-xAsyP1-yBattery, the tunnel junctions of 15- the 4th,
The knot In of 16- the 5thxGa1-xAs batteries, 17-InP cushions, 18-InP substrates, 19-GaInP corrosion barrier layers, 20-GaAs bufferings
Layer, 21-GaAs substrates, 22- impressing glue films, 23- impressing moulds, 24-SiNxFilm.
Embodiment
The specific embodiment of the present invention is elaborated below in conjunction with the accompanying drawings.
As shown in figure 1, a kind of preparation method of quantum dot five-junction solar cell of the invention, comprises the following steps：
(a) the positive joint solar cell of grown InP two of MOCVD epitaxy is passed through；
(b) MOCVD epitaxy back growth GaAs three-joint solar cells are passed through；
(c) joint solar cells of InP two and the knot sun of the GaAs tri- are realized by directly bonding semiconductor technique
The bonding of energy battery；
(d) stripping of sacrifice layer is completed by selective corrosion technique.
Wherein, the sacrifice layer is GaInP etch stop layers 19, GaAs cushions 20 and GaAs substrates 21.
As shown in Fig. 2 the connection solar cells of InP two based on extension forward direction growth, including InP bond contacts layer the 13, the 4th
Tie InxGa1-xAsyP1-yBattery 14, the 4th tunnel junctions 15, the 5th knot InxGa1-xAs batteries 16, InP cushions 17 and InP substrate
18。
It is metal organic chemical vapor deposition technology grown InP cushion successively on InP substrate 18 using MOCVD
17th, the 5th knot InxGa1-xAs batteries 16, the 4th tunnel junctions 15, the 4th knot InxGa1-xAsyP1-yBattery 14, InP bond contacts layer
13, specific preparation process is as follows：
(1) InP substrate 18 adulterated using p-type, thickness is 300-700 μm, and doping concentration is 1 × 1017-1×1018cm-3。
(2) equipment is prepared, into MOCVD epitaxy growth.
(3) epitaxial growth InP cushions 17：Thickness is 0.1-0.3 μm, and growth temperature is 500-800 DEG C.
(4) the knot In of epitaxial growth the 5thxGa1-xAs batteries 16：Based on InP cushions 17 successively epitaxial growth InP back surface fields
Layer, InxGa1-xAs bases, InxGa1-xAs launch sites and InP Window layers, wherein 0.3≤x≤0.8, growth temperature is 500-800
℃；The InP back surface field layers are adulterated for p-type, and thickness is 50-400nm, and doping concentration is 1 × 1017-1×1019cm-3；It is described
InxGa1-xAs bases adulterate for p-type, and thickness is 2000-5000nm, and doping concentration is 1 × 1016-1×1018cm-3；It is described
InxGa1-xAs launch sites are adulterated for n-type, and thickness is 50-400nm, and doping concentration is 1 × 1017-1×1019cm-3；The InP windows
Mouth layer is that n-type doping thickness is 30-200nm, and doping concentration is 1 × 1017-1×1019cm-3。
(5) tunnel junctions 15 of epitaxial growth the 4th：Based on the 5th knot InxGa1-xThe InP of the epitaxial growth n-type successively of As batteries 16
The layer of InP of layer and p-type, growth temperature is 500-800 DEG C, and thickness is 10-100nm, and doping concentration is 1 × 1018-1×
1020cm-3。
(6) the knot In of epitaxial growth the 4thxGa1-xAsyP1-yBattery 14：Based on the 4th tunnel junctions 15 successively epitaxial growth InP back of the body
Field layer, InxGa1-xAsyP1-yBase, InxGa1-xAsyP1-yLaunch site and InP Window layers, wherein 0.3≤x≤0.8,0.3≤y≤
0.7, growth temperature is 500-800 DEG C；The InP back surface field layers are p-type doping, and thickness is 30-300nm, doping concentration is 1 ×
1017-1×1019cm-3；The InxGa1-xAsyP1-yBase is p-type doping, and thickness is 2000-5000nm, doping concentration is 1 ×
1016-1×1018cm-3；The InxGa1-xAsyP1-yLaunch site is n-type doping, and thickness is 50-400nm, doping concentration is 1 ×
1017-1×1019cm-3；The InP Window layers are that n-type doping thickness is 30-200nm, and doping concentration is 1 × 1017-1×
1019cm-3。
(7) epitaxial growth InP bond contacts layer 13：Growth temperature is 500-800 DEG C, and thickness is 100-1000nm, doping
Concentration is 1 × 1018-1×1020cm-3。
As shown in figure 3, be the GaAs three-junction solar batteries grown based on extension negative relational matching, including GaAs bond contacts layer
12nd, the 3rd tunnel junctions 11, base layer 10, quantum dot composite bed 9, quantum dot soakage layer 8, the 3rd knot of the 3rd knot GaAs batteries
The emission layer 7 of GaAs batteries, the Window layer 6 of the 3rd knot GaAs batteries, the second tunnel junctions 5, the second knot AlxGa1-xAs batteries 4,
One tunnel junctions 3, the first knot AlxGa1-xIn0.5P batteries 2, GaAs cap layers 1, GaInP etch stop layers 19, the and of GaAs cushions 20
GaAs substrates 21.
GaAs cushions 20, GaInP etch stop layers 19, GaAs are grown using MOCVD successively on GaAs substrates 21
Cap layers 1, the first knot AlxGa1-xIn0.5P batteries 2, the first tunnel junctions 3, the second knot AlxGa1-xAs batteries 4, the second tunnel junctions 5,
The Window layer 6 of three knot GaAs batteries, the emission layer 7 of the 3rd knot GaAs batteries, quantum dot soakage layer 8, quantum dot composite bed 9,
Base layer 10, the 3rd tunnel junctions 11 and the GaAs bond contacts layer 12 of three knot GaAs batteries, specific preparation process is as follows：
(1) the GaAs substrates 21 adulterated using n-type, its thickness is 300-700 μm, and doping concentration is 1 × 1017-1×
1018cm-3。
(2) equipment is prepared, into MOCVD epitaxy growth.
(3) epitaxial growth GaAs cushions 20：Growth temperature is 500-800 DEG C, and growth thickness is 0.1-0.3 μm.
(4) epitaxial growth GaInP etch stop layers 19, growth temperature is 500-800 DEG C, and growth thickness is 0.1-0.3 μm.
(5) the GaAs cap layers 1 of epitaxial growth n-type doping, growth temperature is 500-800 DEG C, and thickness is 100-500nm, is mixed
Miscellaneous concentration is 1 × 1018-1×1019cm-3。
(6) the first knot of epitaxial growth AlxGa1-xIn0.5P batteries 2：Based on GaAs cap layers 1 successively epitaxial growth AlxGa1- xIn0.5P back surface field layers, AlxGa1-xIn0.5P bases, AlxGa1-xIn0.5P launch sites and AlxGa1-xIn0.5P Window layers, wherein 0.2≤
X≤0.5, growth temperature is 500-800 DEG C；The AlxGa1-xIn0.5P back surface field layers are that p-type doping thickness is 30-200nm, doping
Concentration is 1 × 1017-1×1019cm-3；The AlxGa1-xIn0.5P bases are that p-type doping thickness is 500-2000nm, are adulterated dense
Spend for 1 × 1016-1×1018cm-3；The AlxGa1-xIn0.5P launch sites are that n-type doping thickness is 50-200nm, doping concentration
For 1 × 1017-1×1019cm-3；The AlxGa1-xIn0.5P Window layers are that n-type doping thickness is 30-200nm, and doping concentration is 1
×1017-1×1019cm-3。
(7) the first tunnel junctions of epitaxial growth 3：Based on the first knot AlxGa1-xIn0.5The epitaxial growth n-type successively of P batteries 2
AlxGa1-xIn0.5P layers and the Al of p-typexGa1-xAs layers, wherein 0.2≤x≤0.5, growth temperature is 500-800 DEG C, adulterate dense
Degree is 1 × 1018-1×1020cm-3, thickness is 10-100nm.
(8) the second knot of epitaxial growth AlxGa1-xAs batteries 4：Based on the first tunnel junctions 3 successively epitaxial growth AlxGa1- xIn0.5P back surface field layers, AlxGa1-xAs bases, AlxGa1-xAs launch sites and AlInP Window layers, wherein 0.2≤x≤0.5, growth temperature
Spend for 500-800 DEG C；The AlxGa1-xIn0.5P back surface field layers are p-type doping, and thickness is 30-200nm, doping concentration is 1 ×
1017-1×1019cm-3；The AlxGa1-xAs bases are that p-type doping thickness is 1000-3000nm, and doping concentration is 1 × 1016-1
×1018cm-3；The AlxGa1-xAs launch sites are that n-type doping thickness is 50-200nm, and doping concentration is 1 × 1017-1×
1019cm-3；The AlInP Window layers are adulterated for n-type, and thickness is 30-200nm, and doping concentration is 1 × 1017-1×1019cm-3。
(9) the second tunnel junctions of epitaxial growth 5：Based on the second knot AlxGa1-xThe GaInP of the epitaxial growth n-type successively of As batteries 4
The Al of layer and p-typexGa1-xAs layers, wherein 0.2≤x≤0.5, growth temperature is 500-800 DEG C, doping concentration is 1 × 1018-1×
1020cm-3, thickness is 10-100nm.
(10) Window layer 6 of the knot GaAs batteries of epitaxial growth the 3rd is the Al that n-type is adulteratedxGa1-xAs Window layers, wherein 0.2
≤ x≤0.5, growth temperature is 500-800 DEG C, and thickness is 30-200nm, and doping concentration is 1 × 1017-1×1019cm-3。
(11) emission layer 7 of the knot GaAs batteries of epitaxial growth the 3rd is the GaAs launch sites that n-type is adulterated, and growth temperature is
500-800 DEG C, thickness is 50-200nm, and doping concentration is 1 × 1017-1×1019cm-3。
(12) epitaxially grown quantum dot soakage layer 8 is GaAs layers or InxGa1-xAs layers, 0≤x≤0.1, growth temperature is
500-800 DEG C, thickness is 20-100nm.
(13) nano impression pattern transfer experiment is carried out in thousand grades of ultra-clean chambers, and concrete operation step is shown in Fig. 5.First, will
PMMA particles are dissolved in methyl phenyl ethers anisole, and the mass percent of PMMA particles and methyl phenyl ethers anisole is 10%, and Mw=35K and Mw=is respectively configured
350K PMMA glue；PMMA glue is coated with to the quantum dot soakage layer 8 finished in liner Epitaxial growth, in 180 DEG C of vacuum drying ovens
Middle baking 1.5h, makes PMMA glue thoroughly solidify.It is 1.5 μm to measure film thickness after baking using scanning probe microscopy.Impressing
Pressure limit employed in experiment is 40-50Bar；Imprint temperature scope is 180-230 DEG C；Imprint time scope is 200-
500s, calcining temperature scope is 80-90 DEG C.The dimension of picture of quantum dot is 20-400nm, and depth is 20-1000nm, figure week
Phase is 50-1000nm.
(14) epitaxially grown quantum dot composite bed 9：Epitaxially grown quantum dot and coating successively, the quantum dot are InAs
Or InxGa1-xAs quantum dots, wherein 0≤x≤0.1, growth temperature is 500-800 DEG C, particle size is 20-400nm；It is described to cover
Cap rock includes GaAs layers or GaNAs quantum dot stress compensation coatings；The number of plies of quantum dot is n, wherein 1≤n≤300.
In order that Quantum Dots Growth is better, so before epitaxial growth Quantum Dots Growth, first epitaxial growth buffering
Layer.The growth thickness of the cushion is 5-100nm, and V/III ratios are 20-50, and temperature is 500-600 DEG C；Epitaxial growth afterwards
Quantum dot, the quantum dot deposit thickness is 0.8-3ML, and V/III ratios are 50-200, and its underlayer temperature is 300-550 DEG C；Then
Epitaxial growth coating, the growth thickness of the coating is 5-100nm, and underlayer temperature is 500-600 DEG C；Repeat the quantum
The growth technique step of point and cap rock n times, wherein 1≤n≤300；Finally, continue extension i-GaAs and p-GaAs, and drop
Low V/III is than to promote the cross growth and healing of GaAs films.
It should be noted that V/III ratios described above refer to that N element or As are first in V main groups in the periodic table of chemical element
The content ratio of element and Ga elements or In elements in ii I main groups.
(15) base layer 10 of the knot GaAs batteries of epitaxial growth the 3rd is the GaAs launch sites that p-type is adulterated, and growth temperature is
500-800 DEG C, thickness is 2000-4000nm, and doping concentration is 1 × 1016-1×1018cm-3。
(16) back surface field layer (not marked in Fig. 2) of the knot GaAs batteries of epitaxial growth the 3rd is the Al that p-type is adulteratedxGa1-xAs is carried on the back
Place, wherein 0.2≤x≤0.5, growth temperature is 500-800 DEG C, thickness is 30-200nm, and doping concentration is 1 × 1017-1×
1019cm-3。
(17) tunnel junctions 11 of epitaxial growth the 3rd：The In of n-type is grown to successivelyxGa1-xAs layers and the Al of p-typeyGa1-yAs layers,
Wherein 0≤x≤0.1,0≤y≤0.5, growth temperature is 500-800 DEG C, and thickness is 10-100nm, and doping concentration is 1
×1018-1×1020cm-3。
(18) epitaxial growth GaAs bond contacts layer 12, growth temperature is 500-800 DEG C, and thickness is 100-1000nm, is mixed
Miscellaneous concentration is 1 × 1018-1×1020cm-3。
As shown in figure 4, as obtained by directly bonding semiconductor technique solar battery structure.The growth of extension negative relational matching
Semiconductor nano quantum dot GaAs three-joint solar cells pass through the half of the connection solar cells of InP two that growth is matched with extension forward direction
Conductor Direct Bonding technique connects the battery of two kinds of substrate growths.Directly bonding semiconductor technique is used in the present embodiment
Process conditions be that bonding pressure is 1-5kN, bonding intracavitary gas be nitrogen, bonding temperature be 380 DEG C, temperature change ladder
Degree：Heated up, cooled with 2-8 DEG C/min speed, bonding time is 1.5h with 5-15 DEG C/min speed.
As shown in figure 5, bonding solar cell is peeling off GaAs substrates 21, GaAs cushions 20 and GaInP corrosion stops
The quantum dot five-junction solar cell formed after layer 19.Selective etching stripping technology, uses H2SO4:H2O2Corrode corrosion
GaAs substrates 21, GaAs cushions 20, HCl:H2O=1:1 corrosion corrosion GaInP corrosion barrier layers 19.
As shown in fig. 6, shape and size in order to accurately control quantum dot soakage layer 8, make the quantum dot formation
Energy level is tried one's best unanimously, and uses the method for nanoimprint figure quantum dot soakage layer 8 is formed regular figure.Its concrete operations
Step is：
S1, preparation impressing glue：PMMA particles are dissolved in methyl phenyl ethers anisole, Mw=35K and Mw=350K PMMA is respectively configured
Glue, the PMMA glue is the impressing glue.
S2, preparation impressing glue film 22：The impressing glue is coated with quantum dot soakage layer 8, in 180 DEG C of vacuum drying ovens
Middle baking 1.5h, makes the impressing glue thoroughly solidify to form impressing glue film 22；Impressing glue is measured by scanning probe microscopy
The thickness of film 22 is 1.5 μm.
S3, figure impressing：By above-mentioned sample as in impressing mould 23, entered by 23 pairs of impressing glue films 22 of impressing mould
Row figure is imprinted, wherein, pressure limit is 40-50Bar, and imprint temperature is 180-230 DEG C.
S4, the demoulding：Time to be imprinted, to the impressing mould 23 is opened after 200-500s, completes the demoulding, and calcining temperature is
80-90℃。
S5, remove cull：The impressing sunk part of glue film 22 is removed, until the quantum dot soakage layer 8 of the sunk part
Expose and.
S6, plated film：Layer of sin is deposited on the impressing glue film 22 after removing cullxFilm 24.
S7, stripping：Directly contacted by the impressing glue film 22 of gained sample in S6 and with the top of impressing glue film 22
SiNxFilm 24 is peeled off together.
S8, etching：Gained sample in the S7 is performed etching, wherein, covered with SiNxThe quantum dot infiltration of film 24
Layer 8 etching speed be less than exposed quantum dot soakage layer 8, it is to be etched finish after can obtain the quantum dot with regular figure
Soakage layer 8.
The dimension of picture of quantum dot is 20-400nm in final gained quantum dot soakage layer 8, and the figure cup depth is
20-1000nm, the figure cycle is 50-1000nm.
One embodiment of the present of invention is described in detail above, but the content is only the preferable implementation of the present invention
Example, it is impossible to be considered as the practical range for limiting the present invention.All equivalent changes made according to the present patent application scope and improvement
Deng within the patent covering scope that all should still belong to the present invention.
Claims (7)
1. a kind of preparation method of quantum dot five-junction solar cell, it is characterised in that comprise the following steps：
(a) the positive joint solar cell of grown InP two of MOCVD epitaxy is passed through；
(b) MOCVD epitaxy back growth GaAs three-joint solar cells are passed through；
(c) joint solar cells of InP two and GaAs three-joint solars electricity are realized by directly bonding semiconductor technique
The bonding in pond；
(d) stripping of sacrifice layer is completed by selective corrosion technique, the quantum dot five-junction solar cell is obtained；
The joint solar cells of InP two described in the step (a), successively the extension forward direction growth thickness 0.1-0.3 in InP substrate
μm InP cushions, the 5th knot InxGa1-xAs batteries, the 4th tunnel junctions, the 4th knot InxGa1-xAsyP1-yBattery and thickness 100-
1000nm InP bond contacts layer, wherein 0.3≤x≤0.8,0.3≤y≤0.7；
GaAs three-joint solar cells described in the step (b), successively extension back growth thickness on gaas substrates
0.1-0.3 μm of GaAs cushions, the GaInP corrosion barrier layers of 0.1-0.3 μm of thickness, thickness 100-500nm n-type doping
GaAs cap layers, the first knot AlxGa1-xIn0.5P batteries, the first tunnel junctions, the second knot AlxGa1-xAs batteries, the second tunnel junctions, thickness
The Window layer of 30-200nm the 3rd knot GaAs batteries, emission layer, the thickness 20- of thickness 50-200nm the 3rd knot GaAs batteries
100nm quantum dot soakage layer, quantum dot composite bed, the base layer of thickness 2000-4000nm the 3rd knot GaAs batteries, the 3rd
The GaAs bond contacts layer of tunnel junctions, thickness 100-1000nm, wherein 0.2≤x≤0.5；
The sacrifice layer is the GaAs substrates, the GaAs cushions and the GaInP corrosion barrier layers, the quantum dot leaching
Profit layer is that have regular and equally distributed figure with prepared by nano impression graphical method.
2. the preparation method of quantum dot five-junction solar cell according to claim 1, it is characterised in that in step (c)
Comprise the following steps：
The bonding type intracavitary protected full of nitrogen is placed in after InP bond contacts layer is fitted with GaAs bond contacts layer
It is bonded, completes the bonding of the joint solar cells of InP two and the GaAs three-joint solar cells.
3. the preparation method of quantum dot five-junction solar cell according to claim 1, it is characterised in that in step (d)
Comprise the following steps：
Using GaAs substrates described in corrosion, the GaAs cushions and the GaInP corrosion barrier layers is corroded, complete described sacrificial
The stripping of domestic animal layer.
4. the preparation method of quantum dot five-junction solar cell according to claim 1, it is characterised in that：
The 5th knot In in step (a)xGa1-xAs batteries, the 4th tunnel junctions, the 4th knot InxGa1-xAsyP1-y
Battery includes following growth course respectively：
The 5th knot InxGa1-xAs batteries：Thickness 50-400nm p-type doping InP back surface field layers, thickness 2000- are grown to successively
5000nm p-type doping InxGa1-xThe n-type doping In of As bases, thickness 50-400nmxGa1-xAs launch sites and thickness 30-
200nm n-type doping InP Window layers；4th tunnel junctions：Thickness 10-100nm n-type layer of InP and thickness are grown to successively
10-100nm p-type layer of InP；The 4th knot InxGa1-xAsyP1-yBattery：Thickness 30-300nm p-type doping is grown to successively
InP back surface field layers, thickness 2000-5000nm p-type doping InxGa1-xAsyP1-yThe n-type doping of base, thickness 50-400nm
InxGa1-xAsyP1-yLaunch site and thickness 30-200nm n-type doping InP Window layers.
5. the preparation method of quantum dot five-junction solar cell according to claim 1, it is characterised in that：
First knot Al described in step (b)xGa1-xIn0.5P batteries, first tunnel junctions, the second knot AlxGa1-xAs electricity
Pond, second tunnel junctions, the quantum dot composite bed and the 3rd tunnel junctions include following growth course：
The first knot AlxGa1-xIn0.5P batteries：Thickness 30-200nm p-type doping Al is grown to successivelyxGa1-xIn0.5P back surface fields
The p-type doping Al of layer, thickness 500-2000nmxGa1-xIn0.5The n-type doping Al of P bases, thickness 50-200nmxGa1-xIn0.5P is sent out
Penetrate area and thickness 30-200nm n-type doping AlxGa1-xIn0.5P Window layers；First tunnel junctions：Thickness is grown to successively
10-100nm n-type AlxGa1-xIn0.5The Al of P layers and thickness 10-100nm of p-typexGa1-xAs layers；The second knot AlxGa1- xAs batteries：Thickness 30-200nm p-type doping Al is grown to successivelyxGa1-xIn0.5The p-type of P back surface field layers, thickness 1000-3000nm
Adulterate AlxGa1-xThe n-type doping Al of As bases, thickness 50-200nmxGa1-xAs launch sites and thickness 30-200nm n-type doping
AlInP Window layers；Second tunnel junctions：Thickness 10-100nm GaInP layers of n-type is grown to successively with thickness 10-100nm's
P-type AlxGa1-xAs layers；The quantum dot composite bed：Quantum dot layer and the covering for compensating quantum dot stress are grown to successively
Layer；3rd tunnel junctions：Thickness 10-100nm n-type In is grown to successivelyxGa1-xAs layers and thickness 10-100nm of p-type
AlyGa1-yAs layers；
The first knot AlxGa1-xIn0.5P batteries, first tunnel junctions, the second knot AlxGa1-xAs batteries, described second
0.2≤x≤0.5 in tunnel junctions；
0≤x≤0.1,0≤y≤0.5 in 3rd tunnel junctions.
6. the preparation method of quantum dot five-junction solar cell according to claim 1, it is characterised in that：
The quantum dot soakage layer is GaAs layers or InxGa1-xAs layers；Quantum dot composite bed epitaxially grown quantum dot successively
And coating, the quantum dot is InAs or InxGa1-xAs quantum dots, wherein 0≤x≤0.1.
7. the preparation method of a kind of quantum dot five-junction solar cell to described in claim 1, wherein to quantum dot soakage layer
Nano impression figure is carried out, the nano impression graphical method is implemented in thousand grades of ultra-clean chambers, specifically includes following steps：
S1：Glue：Methyl phenyl ethers anisole is dissolved in by PMMA particles and prepares impressing glue；
S2：Film：Glue is imprinted described in spin coating on the quantum dot soakage layer, impressing glue film is prepared；
S3：Impressing：Sample obtained by step S2 is placed in impressing mould, the impressing glue film entered by the impressing mould
Row figure is imprinted；
S4：The demoulding：The impressing mould is opened after impressing and completes the demoulding；
S5：Remove cull：The impressing glue film sunk part is removed, until the quantum dot soakage layer of the sunk part
Expose and；
S6：Plated film：Imprinted described in S5 on glue film and layer of sin is depositedxFilm；
S7：Peel off：The SiN by glue film is imprinted described in S6 and with directly being contacted above the impressing glue filmxFilm
Peel off in the lump；
S8：Etching：Gained sample in the S7 is performed etching, covered with the SiNxThe etching of the quantum dot soakage layer of film
Speed is less than the quantum dot leaching that can be obtained after the etching speed of exposed quantum dot soakage layer, etching with regular figure
Moisten layer.
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