# US 9,520,515 B2 · Emitter structure based on silicon components to be used in a photovoltaic converter and a method for production of the photovoltaic device

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- Number: US 9,520,515 B2
- Document ID: US9520515B2
- Status: Granted
- Kind: B2
- Application number: 14/003,476
- Filed: 2012-03-22
- Published: 2013-12-26
- Granted: 2016-12-13
- Earliest claimed: 2011-03-25
- Assignees: Segton Adt SAS
- Applicants: Zbigniew Kuznicki; Patrick Meyrueis
- Inventors: Zbigniew Kuznicki; Patrick Meyrueis
- Web page: https://patentgrep.com/patent/US9520515B2

## CPC

- H10F 77/1465: {including only Group IV materials, e.g. Si-SiGe superlattices}
- B82Y 20/00: Nanooptics, e.g. quantum optics or photonic crystals
- H10F 71/10: the devices comprising amorphous semiconductor material
- H10F 71/103: {including only Group IV materials}
- H10F 71/121: {The active layers comprising only Group IV materials}
- H10F 71/128: {Annealing}
- H10F 71/134: {Irradiation with electromagnetic or particle radiation}
- H10F 71/135: {Application of a bias; Current injection}
- H10F 77/122: comprising only Group IV materials
- H10F 77/1462: {comprising amorphous semiconductor layers}
- H10F 77/147: {Shapes of bodies}
- H10F 77/148: {Shapes of potential barriers}
- H10F 77/16: Material structures, e.g. crystalline structures, film structures or crystal plane orientations
- H10F 77/1625: {Semiconductor nanoparticles embedded in semiconductor matrix}
- H10F 77/166: Amorphous semiconductors
- H10F 77/1662: {including only Group IV materials}
- H10F 77/703: {of the semiconductor bodies, e.g. textured active layers}
- H10P 30/204: {into Group IV semiconductors}
- H10P 30/208: {of electrically inactive species}
- H10P 30/21: {of electrically active species}
- H10P 30/28: characterised by an annealing step, e.g. for activation of dopants
- H10P 34/00: Irradiation with electromagnetic or particle radiation of wafers, substrates or parts of devices
- B82Y 40/00: Manufacture or treatment of nanostructures
- Y02E 10/50: Photovoltaic [PV] energy
- Y02E 10/545: Microcrystalline silicon PV cells
- Y02E 10/546: Polycrystalline silicon PV cells
- Y02E 10/547: Monocrystalline silicon PV cells
- Y02E 10/548: Amorphous silicon PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

This invention aims to reduce and preferably to cancel the carrier collection limit effect in order to considerably increase the conversion efficiency. This improvement is achieved by a suitable modification of the amorphized layer thickness or even by discontinuities separating amorphizing beams or amorphized nanopellets.

## Claims

### Claim 1

A photovoltaic device, comprising:
a crystalline silicon base member;
a rear electrode operatively connected to said crystalline silicon base member;
a crystalline silicon emitter member formed from a crystalline silicon mass and having a front face;
a front grid electrode operatively connected to said front face of said crystalline silicon emitter member;
a PN junction between said crystalline silicon base member and said crystalline silicon emitter member;
at least one continuous layer of amorphized silicon material comprising a plurality of substantially separate amorphized silicon regions and disposed within said crystalline silicon mass of said crystalline silicon emitter member; and
at least one pair of nanolayers of crystalline silicon metamaterial, wherein each one of said at least one pair of nanolayers of crystalline silicon metamaterial has an undulating configuration comprising a plurality of trough and crest portions wherein said plurality of trough portions of a first nanolayer of said at least one pair of nanolayers are respectively disposed opposite said plurality of crest portions of a second nanolayer of said at least one pair of nanolayers such that said plurality of trough portions and said plurality of crest portions of said at least one pair of nanolayers substantially surround said plurality of substantially separate amorphized silicon regions so as to separate said at least one layer of amorphized silicon material from said crystalline silicon mass.

### Claim 2 (depends on 1)

The photovoltaic device as set forth in claim 1, wherein:
said first nanolayer of crystalline silicon metamaterial is interposed between said crystalline silicon emitter member and said plurality of substantially separate amorphized silicon regions so as to form a first nanolayer of crystalline silicon metamaterial interface; and
said second nanolayer of crystalline silicon metamaterial is interposed between said crystalline silicon emitter member and said plurality of substantially separate amorphized silicon regions so as to form a second nanolayer of crystalline silicon metamaterial interface,
wherein said at least one layer of said amorphized silicon material is interposed between said first and second nanolayers of crystalline silicon metamaterial.

### Claim 3 (depends on 1)

A photovoltaic device according to claim 1, wherein said at least one layer of amorphized silicon material, comprising said plurality of substantially separate amorphized silicon regions, comprises a plurality of layers of amorphized silicon material wherein each one of said plurality of layers of amorphized silicon material comprises a plurality of amorphized silicon regions.

### Claim 4 (depends on 3)

A photovoltaic device as set forth in claim 3, wherein:
each one of said plurality of layers of amorphized silicon material are disposed substantially parallel to one another.

### Claim 5 (depends on 4)

A photovoltaic device as set forth in claim 4, wherein:
said plurality of amorphized silicon regions define crest and trough portions.

### Claim 6 (depends on 5)

A photovoltaic device as set forth in claim 5, wherein:
said plurality of crest and trough portions of at least one of said plurality of layers of amorphized silicon material are vertically misaligned with respect to said plurality of crest and trough portions defined within another one of said plurality of layers of amorphized silicon material.

### Claim 7 (depends on 6)

A photovoltaic device as set forth in claim 6, wherein:
said plurality of layers of amorphized silicon material comprises three layers of amorphized silicon material disposed parallel to one another; and
said plurality of crest and trough portions of a middle one of said three layers of amorphized silicon material is vertically misaligned with respect to said plurality of crest and trough portions defined within the other two of said three layers of amorphized silicon material.

### Claim 8 (depends on 5)

A photovoltaic device according to claim 5, wherein said plurality of crest and trough portions of each one of said plurality of layers of amorphized silicon material are respectively vertically aligned with said plurality of crest and trough portions defined within all other ones of said plurality of layers of amorphized silicon material.

### Claim 9 (depends on 1)

A photovoltaic device according to claim 1 characterized in that each one of said plurality of substantially separate amorphized silicon regions has a substantially spherical configuration.

### Claim 10 (depends on 1)

A photovoltaic device according to claim 1 characterized in that said at least one pair of nanolayers of crystalline silicon metamaterial comprise doped crystalline silicon.

### Claim 11 (depends on 1)

A photovoltaic device as set forth in claim 1, wherein:
each one of said plurality of substantially separate amorphized silicon regions has a substantially hexagonal configuration.

### Claim 12

A method of making a photovoltaic device, comprising the steps of:
providing a crystalline silicon base member;
operatively connecting a rear electrode to said crystalline silicon base member;
providing a crystalline silicon emitter member formed from a crystalline silicon mass and having a front face;
operatively connecting a front grid electrode to said front face of said crystalline silicon emitter member;
forming a PN junction between said crystalline silicon base member and said crystalline silicon emitter member;
forming at least one continuous layer of amorphized silicon material comprising a plurality of substantially separate amorphized silicon regions by an ion implantation or electron beam irradiation amorphization process and disposed within said crystalline silicon mass of said crystalline silicon emitter member; and
forming at least one pair of nanolayers of crystalline silicon metamaterial, wherein each one of said at least one pair of nanolayers of crystalline silicon metamaterial has an undulating configuration comprising a plurality of trough and crest portions wherein said plurality of trough portions of a first nanolayer of said at least one pair of nanolayers are respectively disposed opposite said plurality of crest portions of a second nanolayer of said at least one pair of nanolayers such that said plurality of trough portions and said plurality of crest portions of said at least one pair of nanolayers substantially surround said plurality of substantially separate amorphized silicon regions so as to separate said at least one layer of amorphized silicon material from said crystalline silicon mass.

### Claim 13 (depends on 12)

The method as set forth in claim 12, wherein:
said formations of said first and second nanolayers of metamaterial are performed by scanning said emitter member with an ion beam or an electron beam.

### Claim 14 (depends on 13)

The method as set forth in claim 13, wherein:
said scanning of said emitter member with said ion beam or electron beam is accomplished in accordance with a scanning pattern comprising a lengthwise passage pattern.

### Claim 15 (depends on 12)

The method as set forth in claim 12, wherein
said first nanolayer of crystalline silicon metamaterial is interposed between crystalline silicon emitter member and said plurality of substantially separate amorphized silicon regions so as to form a first nanolayer of crystalline silicon metamaterial interface; and
said second nanolayer of crystalline silicon metamaterial is interposed between said crystalline silicon emitter member and said plurality of substantially separate amorphized silicon regions so as to form a second nanolayer of crystalline silicon metamaterial interface,
wherein said at least one layer of said amorphized silicon material is interposed between said first and second nanolayers of crystalline silicon metamaterial.

### Claim 16 (depends on 12)

The method as set forth in claim 12, further comprising the step of:
subjecting said at least one pair of nanolayers of metamaterial, formed from said crystalline silicon by said ion implantation or electron beam irradiation, to post implantation or irradiation thermal treatment.

### Claim 17 (depends on 12)

The method according to claim 12 characterized in that ions used for said ion implantation process step are silicon or phosphorous ions.

### Claim 18 (depends on 17)

The method according to claim 17 characterized in that the ion implantation energy ranges from 10 to 300 keV and the dose of ions is between 5×1014 cm−2 and 5×1016 cm−2.

### Claim 19 (depends on 12)

The method according to claim 12 characterized in that the energy of the electron beam ranges from 200 keV to 5 MeV.

### Claim 20 (depends on 12)

The method according to claim 12, further comprising the step of:
subjecting said emitter member to thermal treatment which comprises one initial continuous annealing step followed by at least one cycle of successive discontinuous annealing sequences.

### Claim 21 (depends on 20)

The method according to claim 20 characterized in that said at least one cycle of successive discontinuous annealing sequences is performed within a temperature range of 100° C. to 500° C.

### Claim 22 (depends on 21)

The method according to claim 21 characterized in that each exposure of said emitter member to said annealing sequence at 500° C. lasts from 2 to 5 minutes with a recuperation time of 1 to 4 minutes wherein said at least one cycle of successive discontinuous annealing sequences comprises three to six cycles.

### Claim 23 (depends on 13)

The method according to claim 13 characterized in that said scanning of said emitter member with said ion beam or electron beam is accomplished in accordance with a scanning pattern comprising a crossed passage pattern.

### Claim 24 (depends on 23)

The method according to claim 23 characterized in that said crossed passage pattern is an oblique passage pattern.

### Claim 25

A photovoltaic device, comprising:
a crystalline silicon base member;
a rear electrode operatively connected to said crystalline silicon base member;
a crystalline silicon emitter member formed from a crystalline silicon mass and having a front face;
a front grid electrode operatively connected to said front face of said crystalline silicon emitter member;
a PN junction between said crystalline silicon base member and said crystalline silicon emitter member;
at least one discontinuous layer of amorphized silicon material comprising a plurality of separate amorphized silicon regions and disposed within said crystalline silicon mass of said crystalline silicon emitter member; and
a plurality of nanolayers of crystalline silicon metamaterial respectively entirely surrounding said plurality of separate amorphized silicon regions on all sides so as to separate and isolate said plurality of separate amorphized silicon regions from each other and from said crystalline silicon mass of said crystalline silicon emitter member.

### Claim 26 (depends on 25)

A photovoltaic device as set forth in claim 25, wherein:
each one of said plurality of separate amorphized silicon regions has a substantially hexagonal configuration.

### Claim 27 (depends on 25)

A photovoltaic device as set forth in claim 25, wherein:
each one of said plurality of separated amorphized silicon regions has a substantially spherical configuration.

### Claim 28

A method of making a photovoltaic device, comprising the steps of:
providing a crystalline silicon base member;
operatively connecting a rear electrode to said crystalline silicon base member;
providing a crystalline silicon emitter member formed from a crystalline silicon mass and having a front face;
operatively connecting a front grid electrode to said front face of said crystalline silicon emitter member;
forming a PN junction between said crystalline silicon base member and said crystalline silicon emitter member;
forming at least one discontinuous layer of amorphized silicon material comprising a plurality of separate amorphized silicon regions disposed within said crystalline silicon mass of said crystalline silicon emitter member; and
forming a plurality of nanolayers of crystalline silicon metamaterial respectively entirely surrounding said plurality of separate amorphized silicon regions on all sides so as to separate and isolate said plurality of separate amorphized silicon regions from each other and from said crystalline silicon mass of said crystalline silicon emitter member.

### Claim 29 (depends on 28)

The method as set forth in claim 28, wherein:
each one of said plurality of separate amorphized silicon regions has a substantially hexagonal configuration.

### Claim 30 (depends on 28)

The method as set forth in claim 28, wherein:
each one of said plurality of separate amorphized silicon regions has a substantially spherical configuration.