CN105280745B - Tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge and preparation method thereof - Google Patents
Tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge and preparation method thereof Download PDFInfo
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- Y02E10/544—Solar cells from Group III-V materials
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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
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Abstract
This application discloses a kind of four knot cascade solar cells and preparation method thereof, the tri- knot sun of GaInP/GaAs/InGaAs and Ge solar cells that are grown based on inverted structure are subjected to single-chip integration, it is respectively the solar cell of 1.9/1.4/1.0/0.67eV to realize four knot band-gap energies.The present invention makes it effectively to suppress bonded interface electrical loss and light loss using the graphene bonding face with special construction form, the excellent electric conductivity of graphene bonding face and translucency, its ductility helps to discharge stress.Therefore four statement of account piece efficient solar batteries being prepared can obtain high voltage, low current output, so as to effectively reduce the ohmic loss in super-high power concentrator solar cell, obtain higher transfer efficiency.
Description
Technical field
The application belongs to solar-photovoltaic technology field, more particularly to a kind of tetra- knots of GaInP/GaAs/InGaAs/Ge
Cascade solar cell and preparation method thereof.
Background technology
In photovoltaic technology, the photoelectric conversion efficiency for improving solar cell is that it reduces a kind of effective hand of cost of electricity-generating
Section, can promote the further practical of solar cell.The solar battery structure of more knot tandem types is using different energy gaps
Sub- battery series connection drastically increases the utilization to sunlight, so as to significantly improve the efficiency of solar cell.At present research compared with
More and more mature technology systems are tri- junction batteries of GaInP/GaAs/Ge.Tri- knots of GaInP/ (In) GaAs/Ge in 2007
The average efficiency of tandem solar cell large-scale production is already close to 30%.Under 240 times of optically focused, this multi-junction solar
The lab A M1.5D efficiency of battery has been over 40%.The Eicke Weber religions of fraunhofer research institute of Germany at present
Three knot GaInP/GaInAs/Ge efficiency of solar cell have been brought up to 41.1% by the research group for awarding leader.But should
Ge bottoms battery covers wider spectrum in three junction batteries, its short circuit current flow is larger, in order to realize the electric current with other sub- batteries
With sun light utilization efficiency will necessarily be reduced.
For in theory, knot number is more, and efficiency is higher.According to Shockley-Quisser models, four knot band-gap energies are
1.9/1.4/1.0/0.67eV solar cell can obtain the transfer efficiency more than 45%.Simultaneously as four junction structures more can
Enough realize high voltage, low current output, can effectively reduce the resistance heat loss in super-high power concentrator solar cell, and surpass
High power concentrator battery can greatly reduce solar cell cost, so as to exist for III-V compound semiconductor solar cells
Progress in terms of industrialization, which plays, greatly to be promoted.Based on limitation of the solar cell of lattice mismatch on Material growth and
The needs of four knot above battery developments, realize that the direct monolithic of big mismatched lattices material is more by the method for extension Direct Bonding
Junction battery, which integrates, has been proved to possess very big potentiality.
In the development of four junction batteries, the scientists of U.S.'s Boeing-spectrum company and Caltech are proposed Ge
The side of InGaAsP/InGaAs (1.0/0.72eV) bondings grown on binode GaInP/GaAs batteries and InP substrate on substrate
Method, to realize that four knot GaInP/GaAs/ of monolithic [Ge/InP is bonded interface]/InGaAsP/InGaAs is integrated.Although use
The material structure of Lattice Matching, but Ge/InP can absorb sunlight of the energy in below 1.42eV, so as to reduce InGaAsP/
The efficiency of InGaAs batteries.Bonding between semi-conducting material is by semi-conducting material doping concentration and rough surface at bonded interface
The influence of degree, cleannes etc., can produce certain electrical losses and optical loss in bonded interface, so as to reduce solar cell effect
Rate.
The content of the invention
It is respectively 1.9/ the purpose of the present invention is to propose to a kind of band-gap energy for the deficiencies in the prior art mentioned above
1.4/1.0/0.67eV four knot GaInP/GaAs/InGaAs/Ge solar cells and preparation method thereof.
To achieve the above object, the present invention provides following technical solution：
The embodiment of the present application discloses a kind of photoelectric device, including the first semiconductor layer and the second semiconductor layer, and described
Semi-conductor layer is bonded by bonded layer with second semiconductor layer, and the bonded layer is graphene film.
Correspondingly, the embodiment of the present application also discloses a kind of production method of photoelectric device, including step：
S1, by growing substrate of metal foil prepare graphene film；
S2, make transfer medium on graphene film；
S3, remove metal foil, and transfer medium/graphene film is pasted on the bonding face of the first semiconductor layer；
S4, remove transfer medium, the bonding face of the second semiconductor layer is bonded with graphene film, then in vacuum chamber
It is bonded.
The embodiment of the present application also discloses a kind of tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge, GaInP/
It is bonded between GaAs/ InGaAs three-junction solar batteries and unijunction Ge solar cell chips by graphene film.
Preferably, in above-mentioned tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge, the graphene film
Thickness be 0.34 ~ 30nm.
Correspondingly, the embodiment of the present application also discloses a kind of tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge
Production method, including step：
S1, by growing substrate of metal foil prepare graphene film；
S2, make transfer medium on graphene film；
S3, remove metal foil, and transfer medium/graphene film is pasted the tri- knot sun of GaInP/GaAs/ InGaAs
On the bonding face of battery；
S4, remove transfer medium, the bonding face of unijunction Ge solar cell chips is bonded with graphene film, then true
It is bonded in empty room.
Preferably, it is described in the production method of above-mentioned tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge
The material of metal foil is selected from Cu, Ni or Ru.
Preferably, it is described in the production method of above-mentioned tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge
The material of transfer medium is selected from polymethyl methacrylate, dimethyl silicone polymer or adhesive tape.
Preferably, in the production method of above-mentioned tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge, specifically
Including step：
（1）, on gaas substrates grow Ga successively according to the direction away from GaAs substrates0.51In0.49P top cells, GaAs
Intermediate layer battery, GaxIn1-xP buffer transition layers, In0.27Ga0.73As bottom cells and Ga0.25InP back surface layers, form
GaInP/GaAs/ InGaAs three-junction solar batteries, wherein 0 ＜ x ＜ 0.26；
（2）The pn single junction cells of Ge are formed by the method for phosphorus diffusion on p-type Ge substrates, and on GaInP nucleating layers,
Surface covers of the GaAs battery is grown, forms unijunction Ge solar cell chips；
（3）Graphene film is prepared using chemical vapour deposition technique, and by growing substrate of metal foil；
（4）Transfer medium is coated on graphene film；
（5）Metal substrate with transfer medium and graphene film is put into corrosive liquid to fall metal erosion；
（6）The film of transfer medium/graphene is pulled out from corrosive liquid, after cleaning, pastes three knot GaInP/GaAs/
The surface cover of InGaAs solar cell epitaxial wafers or the Ga of unijunction Ge solar cell chips0.25InP back surface layers；
（7）Transfer medium is removed, and is annealed, obtains graphene bonding face；
（8）The epitaxial wafer of GaInP/GaAs/InGaAs three-junction solar batteries and unijunction Ge solar cell chips are positioned over
In vacuum chamber, vacuum 10-4~10-5Pa, by the epitaxial wafer of GaInP/GaAs/InGaAs three-junction solar batteries with unijunction Ge too
Positive battery wafer is bonded and applies 30 ~ 50N/cm2Pressure, keep 1 ~ 2 it is small when, vacuum chamber is heated to 150 ~ 200 DEG C, to tight
The chip of closely connected conjunction is to uniformly applying 100 ~ 150 N/cm2Pressure, keep 1 ~ 2 it is small when.
Preferably, in the production method of above-mentioned tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge, also wrap
Include step：
（9）Para-linkage obtains four-junction solar battery and is heat-treated：It is first heated to 350 ~ 400 DEG C and insulation 2 ~ 3 is small
When, wherein, when temperature is more than 200 DEG C, the speed of heating is 0.2 ~ 0.5 DEG C/min；Finally, using rate of temperature fall as 0.2 ~
0.5 DEG C/min carries out cooling processing, wherein, when temperature be less than 100 DEG C, room temperature is cooled to by the way of Temperature fall.
Preferably, it is described in the production method of above-mentioned tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge
GaxIn1-xP buffer transition layers use the growing method of content gradually variational, i.e., after GaAs intermediate layers battery has been grown, growth 10
The different GaInP cushions of layer Ga components, by the growth of this 10 layers of cushions, finally grow a layer lattice constant and
In0.27Ga0.73GaInP identical As.
Compared with prior art, the advantage of the invention is that：
The graphene bonding face that the present invention uses is a kind of cycle honeycomb-like network structure, its basic structural unit is organic
Most stable of benzene hexatomic ring in material, lacks without carbon atom, and the connection between each carbon atom is very flexible.In the bonding face
Each carbon atom is sp2 hydridization, and contributes and electronically form big pi bond on a remaining p track, and pi-electron can move freely,
Therefore graphene bonding face has than traditional conductor and semiconductor（Such as silicon and copper）More good electric conductivity, so that effectively
Inhibit interface electrical losses.In addition, the structural form that graphene bonding face is special so that it has good translucency at the same time
（The hexagonal carbon atom material of individual layer only absorbs 2.3% light）With certain ductility（~ 20% can be stretched）, reducing boundary
While the light loss of face, it helps release stress, improves bonded interface quality.Therefore four statement of account pieces that are prepared are efficiently too
Positive electricity pond can obtain high voltage, low current output, so that the ohmic loss in super-high power concentrator solar cell is effectively reduced,
Obtain higher transfer efficiency.
Brief description of the drawings
In order to illustrate the technical solutions in the embodiments of the present application or in the prior art more clearly, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments described in application, for those of ordinary skill in the art, without creative efforts,
Other attached drawings can also be obtained according to these attached drawings.
Fig. 1 show the method flow diagram that four knot cascade solar cells make in the specific embodiment of the invention；
Fig. 2 show the schematic diagram of graphene bonding face in the specific embodiment of the invention；
Fig. 3 show the structure diagram of four knot cascade solar cells obtained in the specific embodiment of the invention；
Fig. 4 show the preparation process schematic diagram of four knot cascade solar cells in the specific embodiment of the invention.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with the accompanying drawings to the specific reality of the present invention
The mode of applying is described in detail.The example of these preferred embodiments is illustrated in the accompanying drawings.Shown in attached drawing and according to
What the embodiments of the present invention of attached drawing description were merely exemplary, and the present invention is not limited to these embodiments.
Here, it should also be noted that, in order to avoid having obscured the present invention because of unnecessary details, in the accompanying drawings only
Show the structure and/or processing step closely related with scheme according to the present invention, and eliminate little with relation of the present invention
Other details.
With reference to shown in Fig. 1, by taking tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge as an example, it is introduced below this four
The production method for tying cascade solar cell, its production method include step：
s1：The growth of battery before bonding（Carried out in MOCVD or MBE systems）
（1）As shown in figure 4, under 600 ~ 700 DEG C of high temperature, unijunction Ge solar cell chips are to pass through phosphorus on p-type Ge substrates
The method of diffusion forms the pn single junction cells of Ge, and on GaInP nucleating layers, surface covers of the growth GaAs battery.
（2）As shown in figure 4, GaInP/GaAs/InGaAs three-junction solar batteries are prepared using inverted growing method
, i.e., Ga is grown successively according to the direction away from GaAs substrates on gaas substrates0.51In0.49P top cells, GaAs intermediate layers
Battery, GaxIn1-xP buffer transition layers（X is more than 0, and less than 0.26）、In0.27Ga0.73As bottom cells, Ga0.25InP carries on the back table
Surface layer.Wherein GaxIn1-xP buffer transition layers use content gradually variational growing method, i.e., grown GaAs intermediate cells it
Afterwards, the different GaInP cushions of 10 layers of Ga components are grown, by the growth (thickness is 2 μm) of this 10 layers of cushions,
Finally grow a layer lattice constant and In0.27Ga0.73GaInP identical As, effectively release stress, reduction are non-in this way for profit
Radiation recombination.
：The preparation of graphene bonding face
（1）Chemical vapour deposition technique (CVD) is used first, and prepares graphene film using Cu metal foils as growing substrate.
The metals such as Ni, Ru can also be used in growing substrate；
（2）Transfer medium polymethyl methacrylate is coated on graphene using the methods of spin coating, rolling（PMMA）.
Dimethyl silicone polymer (PDMS), adhesive tape etc. can be used to be used as transfer medium；
（3）Metal substrate with transfer medium and graphene film is put into metal erosion in suitable corrosive liquid
Fall, obtain swimming in the film of transfer medium/graphene of solution surface.The corrosive liquid of selection has FeCl3Solution（Corrode metal
Cu etc.）.Also acid solution can be used（Corrode W metal etc.）Deng；
（4）The film of transfer medium/graphene is pulled out from corrosive liquid, after cleaning, pastes three knot GaInP/GaAs/
The surface cover of InGaAs solar cell epitaxial wafers（GaAs）Or the back surface layer of unijunction Ge solar cell chips（Ga0.25InP）；
（5）Transfer medium PMMA, and the 3h that anneals are removed with organic solvent-acetone etc., obtains the stone that thickness is 0.34-30nm
Black alkene bonding face.
：Bonding chip
（1）By the epitaxial wafer of GaInP/GaAs/InGaAs three-junction solar batteries and unijunction Ge solar cell chips
Cleaning is learned, surface organic matter is removed, is moved into after dry in vacuum chamber；
（2）Under conditions of vacuum chamber is room temperature, by the epitaxial wafer and list of GaInP/GaAs/InGaAs three-junction solar batteries
Knot Ge solar cell chips are bonded and apply 30 ~ 50N/ cm2Pressure, keep 1 ~ 2 it is small when；
（3）Vacuum chamber is heated to 150 ~ 200 DEG C, 100 ~ 150 N/ cm are applied to uniform to the chip fitted closely2
Pressure, keep 1 ~ 2 it is small when；
（4）Four knot GaInP/GaAs/InGaAs/Ge solar cells are positioned in the gaseous environment of argon gas or nitrogen and are carried out
Step back processing；First, when being heated to 350 ~ 400 DEG C and small insulation 2 ~ 3, wherein, when temperature is more than 2000 DEG C, heating
Speed is 0.2 ~ 0.5 DEG C/min；Finally, cooling processing is carried out using rate of temperature fall as 0.2 ~ 0.5 DEG C/min, wherein, work as temperature
Degree is less than 100 DEG C, and room temperature is cooled to by the way of Temperature fall.
：The stripping of substrate and battery process
After bonding, using selective corrosion, by the GaAs substrate desquamations in three junction batteries,
In addition, this method further includes the stripping of the GaAs substrates in three junction batteries, made on the surface of four junction battery of gained
Positive and negative electrode and antireflective film, according to suitable for the packaging technology step of installation to complete the making of four-junction solar battery.
Using translucency, electric conductivity and the ductility that graphene is good in this implementation, it is applied to GaInP/GaAs/
Being bonded between InGaAs three-junction solar batteries and unijunction Ge solar cell chips, the efficient sun electricity of four statement of account pieces being prepared
Pond can obtain high voltage, low current output so that effectively reduce super-high power concentrator solar cell in ohmic loss, obtain compared with
High transfer efficiency.
In other embodiments, graphene film be also used as bonding between other multijunction solar cells and
Bonding in other photoelectric devices such as detector.
Finally, it is to be noted that, term " comprising ", "comprising" or its any other variant be intended to it is non-exclusive
Property includes, so that process, method, article or equipment including a series of elements not only include those key elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Key element.
Claims (7)
1. a kind of production method of tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge, it is characterised in that including following
Step：
(1), Ga is grown successively according to the direction away from GaAs substrates on gaas substrates0.51In0.49Among P top cells, GaAs
Layer battery, GaxIn1-xP buffer transition layers, In0.27Ga0.73As bottom cells and Ga0.25InP back surface layers, form GaInP/
GaAs/InGaAs three-junction solar batteries, wherein 0 ＜ x ＜ 0.26；
(2) the pn single junction cells of Ge are formed by the method for phosphorus diffusion on p-type Ge substrates, and on GaInP nucleating layers, growth
Surface covers of the GaAs battery, forms unijunction Ge solar cell chips；
(3) chemical vapour deposition technique is used, and graphene film is prepared by growing substrate of metal foil；
(4) transfer medium is coated on graphene film；
(5) metal substrate with transfer medium and graphene film is put into corrosive liquid to fall metal erosion；
(6) film of transfer medium/graphene is pulled out from corrosive liquid, after cleaning, pastes three knot GaInP/GaAs/
The surface cover of InGaAs solar cell epitaxial wafers or the Ga of unijunction Ge solar cell chips0.25InP back surface layers；
(7) transfer medium is removed, and is annealed, obtains graphene bonding face；
(8) epitaxial wafer of GaInP/GaAs/InGaAs three-junction solar batteries and unijunction Ge solar cell chips are positioned over vacuum
In room, vacuum 10-4~10-5Pa, by the epitaxial wafer of GaInP/GaAs/InGaAs three-junction solar batteries and the unijunction Ge sun
Battery wafer is bonded and applies 30~50N/cm2Pressure, keep 1~2 it is small when, vacuum chamber is heated to 150~200 DEG C, it is right
The chip fitted closely is to uniformly applying 100~150N/cm2Pressure, keep 1~2 it is small when.
2. the production method of tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge according to claim 1, it is special
Sign is：The material of the metal foil is selected from Cu, Ni or Ru.
3. the production method of tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge according to claim 1, it is special
Sign is：The material of the transfer medium is selected from polymethyl methacrylate, dimethyl silicone polymer or adhesive tape.
4. the production method of tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge according to claim 1, it is special
Sign is, further includes step：
(9) para-linkage obtains four-junction solar battery and is heat-treated：When being first heated to 350~400 DEG C and small insulation 2~3, its
In, when temperature is more than 200 DEG C, the speed of heating is 0.2~0.5 DEG C/min；Finally, using rate of temperature fall as 0.2~0.5 DEG C/
Minute cooling processing is carried out, wherein, when temperature is less than 100 DEG C, room temperature is cooled to by the way of Temperature fall.
5. the production method of tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge according to claim 4, it is special
Sign is：The GaxIn1-xP buffer transition layers use the growing method of content gradually variational, that is, are growing GaAs intermediate layers battery
Afterwards, the different GaInP cushions of 10 layers of Ga components are grown, by the growth of this 10 layers of cushions, finally grow a layer crystal lattice
Constant and In0.27Ga0.73GaInP identical As.
6. tetra- knots of the GaInP/GaAs/InGaAs/Ge cascade sun made using claim 1 to 5 any one of them method
Battery, it is characterised in that：Pass through graphite between GaInP/GaAs/InGaAs three-junction solar batteries and unijunction Ge solar cell chips
Alkene film is bonded.
7. tetra- knot cascade solar cells of GaInP/GaAs/InGaAs/Ge according to claim 6, it is characterised in that：It is described
The thickness of graphene film is 0.34~30nm.
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| CN114171615B (en) * | 2021-11-10 | 2023-12-29 | 江苏华兴激光科技有限公司 | Silicon-based multi-junction solar cell and gradual change buffer layer thereof |
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