U.S. patent application number 11/782969 was filed with the patent office on 2008-03-06 for hybrid solar cells with thermal deposited semiconductive oxide layer.
This patent application is currently assigned to Sony Deutschland GmbH. Invention is credited to Gabrielle Nelles, Hans-Werner Schmidt, Christoph Schmitz, Mukundan Thelakkat, Akio Yasuda.
Application Number | 20080053525 11/782969 |
Document ID | / |
Family ID | 8170479 |
Filed Date | 2008-03-06 |
United States Patent
Application |
20080053525 |
Kind Code |
A1 |
Nelles; Gabrielle ; et
al. |
March 6, 2008 |
HYBRID SOLAR CELLS WITH THERMAL DEPOSITED SEMICONDUCTIVE OXIDE
LAYER
Abstract
The present invention relates to hybrid solar cells having a
semiconducting oxide layer which is vapor deposited on a
substrate.
Inventors: |
Nelles; Gabrielle;
(Stuttgart, DE) ; Yasuda; Akio; (Stuttgart,
DE) ; Schmidt; Hans-Werner; (Bayreuth, DE) ;
Thelakkat; Mukundan; (Bayreuth, DE) ; Schmitz;
Christoph; (Frankfurt, DE) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Sony Deutschland GmbH
Berlin
DE
10785
|
Family ID: |
8170479 |
Appl. No.: |
11/782969 |
Filed: |
July 25, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10799257 |
Mar 12, 2004 |
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11782969 |
Jul 25, 2007 |
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09989848 |
Nov 21, 2001 |
6706962 |
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10799257 |
Mar 12, 2004 |
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Current U.S.
Class: |
136/265 ;
136/252 |
Current CPC
Class: |
H01L 51/0078 20130101;
H01G 9/2031 20130101; Y02E 10/542 20130101; Y02P 70/521 20151101;
H01L 51/0053 20130101; H01L 51/001 20130101; H01L 51/4226 20130101;
H01L 2251/308 20130101; Y02E 10/549 20130101; Y02P 70/50
20151101 |
Class at
Publication: |
136/265 ;
136/252 |
International
Class: |
H01L 31/04 20060101
H01L031/04; H01L 31/0264 20060101 H01L031/0264 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 24, 2000 |
EP |
00125784 |
Claims
1. A hybrid solar cell, wherein hybrid solar cell is produced by a
method comprising introducing a semiconducting oxide layer (SOL) on
a substrate by thermal deposition.
2. The hybrid solar cell according to claim 1, wherein said hybrid
solar cell has a thickness of the complete cell of about 100
nm.
3. The hybrid solar cell according to claim 1, wherein said hybrid
solar cell has an efficiency of about 0.7 to about 1.3% measured at
60 mW/cm .
4. The hybrid solar cell according to claim 1, wherein said hybrid
solar cell is flexible.
5. The hybrid solar cell according to claim 1, wherein said SOL
layer is vapor-deposited.
6. The hybrid solar cell according to claim 1, wherein said method
further comprises deposition and/or vapour-deposition of an
additional layer of lithium fluoride close to the EM interfaces
either on one side or both sides.
7. The hybrid solar cell according to claim 6, wherein the
additional layer has a thickness of between about 0.1 .ANG. to
about 50 .ANG..
8. The hybrid solar cell according to claim 1, wherein said method
further comprises increasing the surfaces of the interfaces of the
layers by use of structured indium tin oxide, co-evaporation of HTM
and dye and/or dye/TiO.sub.2 or co-evaporation of HTM and a
dopant.
9. The hybrid solar cell according to claim 1, wherein said
substrate is selected from the group consisting of glass, coated
glass, polymeric foils, norbornene-based foils, SnO.sub.2-coated
metal foils and stainless steel foils.
10. The hybrid solar cell according to claim 1, wherein said hybrid
solar cell comprises an electrode material which is selected from
the group consisting of indium tin oxide, fluorine doped tin oxide,
zinc oxide, and metal-doped zinc oxide, wherein said metal is
selected from the ground consisting of Au, Al, Ca, Mg, and
combinations thereof.
11. The hybrid solar cell according to claim 10, wherein said
electrode material is indium tin oxide.
12. The hybrid solar cell according to claim 1, wherein said hybrid
solar cell comprises a hole transport material selected from the
group consisting of phthalocyanine and derivatives thereof (with or
without a central atom or group of atoms), metal-free and metal
containing porphyrins and derivatives thereof, TPD derivatives,
triphenylamine and its derivatives, (including different ground
structure as TDATAs, TTABs, TDABs, and cyclic variations like
N-carbazoles and its derivatives), thiophenes, polythiophenes and
derivatives thereof, polyanilines and derivatives thereof and
hexa-benzocoronene and its derivatives, triphenyldiamine
derivatives, aromatic diamine compounds having connected tertiary
aromatic amine units of
1,-bis(4-(di-p-tolylamino)phenyl)-cyclohexane, aromatic diamines
containing two or more tertiary amines and having two or more fused
aromatic rings substituted on the nitrogen atoms, aromatic trimers
having a starburst structure derived from triphenylbenzene,
aromatic diamines, triphenylamine derivatives whose molecule is
sterically asymmetric as a whole, compounds having a plurality of
aromatic diamino groups substituted on a pyrenyl group, aromatic
diamines having tertiary amine units connected through an ethylene
group, aromatic diamines having a styryl structure, starburst type
aromatic triamines, benzyl-phenyl compounds, compounds having
tertiary amine units connected through a fluorene group, triamine
compounds, bisdipyridylaminobiophenyl compounds,
N,N,N-triphenylamine derivatives; aromatic diamines having a
phenoxazine structure, diaminophenylanthridine, and other carbazole
derivatives, hydrazoen compounds, silazane compounds, silanamine
derivatives, phosphamine derivatives, quinacridone compounds,
stilbene compounds, triazole derivatives, oxadiazole derivatives,
imidazole derivatives, polyarylalkane derivatives, pyrazoline
derivatives, pyrazolone derivatives, oxadiazole derivatives,
imidazole derivatives, polyarylalkane derivatives, pyrazoline
derivatives, amino-substituted chalcone derivatives, oxazole
derivatives, styrylanthracene derivatives, fluorenone derivatives
and polysilane derivatives, all compounds alone or in admixture of
two or more, polymers, polyphosphazenes, polyamides, polyvinyl
triphenylamine, polymers having a triphenylamine skeleton, polymers
having triphenylamine units connected through a methylene group and
polymethacrylates containing aromatic amine.
13. The hybrid solar cell according to claim 12, wherein said hole
transport material is copper-phthalocyanine (CuPc).
14. The hybrid solar cell according to claim 12, wherein the
substance of said hole transport material is doped.
15. The hybrid solar cell according to claim 1, wherein said SOL is
a semiconducting oxide
16. The hybrid solar cell according to claim 1, wherein said SOL is
selected from the group consisting of TiO.sub.2, SnO.sub.2, ZnO,
Sb.sub.2O.sub.3, and PbO.
17. The hybrid solar cell according to claim 1, wherein said SOL is
TiO.sub.2.
18. The hybrid solar cell according to claim 1, wherein said hybrid
solar cell comprises a dye is selected from the group consisting of
di- or monosubstituted perylenes with all possible substituents,
terrylene, quinacridone, anthraquinone, nealred,
titanylphthalocyanine, porphines and porphyrines and derivatives
thereof, polyfluorenes and derivatives thereof and azo-dyes.
19. The hybrid solar cell according to claim 1, wherein a dye layer
is deposited in a thickness of about 5 to about 65 nm and the SOL
is deposited in a thickness of about 5 to about 50 nm.
20. The hybrid solar cell according to claim 1, wherein said cell
comprises more than one dye.
21. A hybrid solar cell, wherein hybrid solar cell has the general
structure Substrate+EM/HTM/dye/SOL/EM, or
Substrate+EM/SOL/dye/HTM/EM, or Substrate+EM/HTM/SOL/EM, in which
EM is an electrode material, selected from the group consisting of
a transparent conductive oxide (TCO) and metal, with at least one
of the EM layers of the cell being a TCO, HTM is a hole transport
material, SOL is a semiconducting oxide layer, "dye" means a suited
dye, and wherein said method comprises vapor-deposition of the SOL
of the hybrid organic solar cell.
22. The hybrid solar cell according to claim 21, wherein said
hybrid solar cell has an efficiency of about 0.7 to about 1.3%
measured at 60 mW/cm.sup.2.
23. The hybrid solar cell according to claim 21, wherein said
hybrid solar cell is flexible.
24. The hybrid solar cell according to claim 21, wherein said
method further comprises vapor-deposition of at least one second
layer of the hybrid organic solar cell in addition to the SOL
layer.
25. The hybrid solar cell according to claim 21, wherein said
method further comprises deposition and/or vapour-deposition of an
additional layer of lithium fluoride close to the EM interfaces
either on one side or both sides.
26. The hybrid solar cell according to claim 25, wherein the
additional layer has a thickness of between about 0.1 .ANG. to
about 50 .ANG..
27. The hybrid solar cell according to claim 21, wherein said
method further comprises increasing the surfaces of the interfaces
of the layers by use of structured indium tin oxide, co-evaporation
of HTM and dye and/or dye/TiO.sub.2 or co-evaporation of HTM and a
dopant.
28. The hybrid solar cell according to claim 21, wherein said
substrate is selected from the group consisting of glass, coated
glass, polymeric foils, norbornene-based foils, SnO.sub.2-coated
metal foils and stainless steel foils.
29. The hybrid solar cell according to claim 21, wherein said
electrode material is selected from the group consisting of indium
tin oxide, fluorine doped tin oxide, zinc oxide, and metal-doped
zinc oxide, wherein said metal is selected from the ground
consisting of Au, Al, Ca, Mg, and combinations thereof.
30. The hybrid solar cell according to claim 29, wherein said
electrode material is indium tin oxide.
31. The hybrid solar cell according to claim 21, wherein said hole
transport material selected from the group consisting of
phthalocyanine and derivatives thereof (with or without a central
atom or group of atoms), metal-free and metal containing porphyrins
and derivatives thereof, TPD derivatives, triphenylamine and its
derivatives, (including different ground structure as TDATAs,
TTABs, TDABs, and cyclic variations like N-carbazoles and its
derivatives), thiophenes, polythiophenes and derivatives thereof,
polyanilines and derivatives thereof and hexa-benzocoronene and its
derivatives, triphenyldiamine derivatives, aromatic diamine
compounds having connected tertiary aromatic amine units of
1,-bis(4-(di-p-tolylamino)phenyl)-cyclohexane, aromatic diamines
containing two or more tertiary amines and having two or more fused
aromatic rings substituted on the nitrogen atoms, aromatic trimers
having a starburst structure derived from triphenylbenzene,
aromatic diamines, triphenylamine derivatives whose molecule is
sterically asymmetric as a whole, compounds having a plurality of
aromatic diamino groups substituted on a pyrenyl group, aromatic
diamines having tertiary amine units connected through an ethylene
group, aromatic diamines having a styryl structure, starburst type
aromatic triamines, benzyl-phenyl compounds, compounds having
tertiary amine units connected through a fluorene group, triamine
compounds, bisdipyridylaminobiophenyl compounds,
N,N,N-triphenylamine derivatives; aromatic diamines having a
phenoxazine structure, diaminophenylanthridine, and other carbazole
derivatives, hydrazoen compounds, silazane compounds, silanamine
derivatives, phosphamine derivatives, quinacridone compounds,
stilbene compounds, triazole derivatives, oxadiazole derivatives,
imidazole derivatives, polyarylalkane derivatives, pyrazoline
derivatives, pyrazolone derivatives, oxadiazole derivatives,
imidazole derivatives, polyarylalkane derivatives, pyrazoline
derivatives, amino-substituted chalcone derivatives, oxazole
derivatives, styrylanthracene derivatives, fluorenone derivatives
and polysilane derivatives, all compounds alone or in admixture of
two or more, polymers, polyphosphazenes, polyamides, polyvinyl
triphenylamine, polymers having a triphenylamine skeleton, polymers
having triphenylamine units connected through a methylene group and
polymethacrylates containing aromatic amine.
32. The hybrid solar cell according to claim 31, wherein said hole
transport material is copper-phthalocyanine (CuPc).
33. The hybrid solar cell according to claim 31, wherein the
substance of said hole transport material is doped.
34. The hybrid solar cell according to claim 21, wherein said SOL
is a semiconducting oxide
35. The hybrid solar cell according to claim 21, wherein said SOL
is selected from the group consisting of TiO.sub.2, SnO.sub.2, ZnO,
Sb.sub.2O.sub.3, and PbO.
36. The hybrid solar cell according to claim 21, wherein said SOL
is TiO.sub.2.
37. The hybrid solar cell according to claim 21, wherein said dye
is selected from the group consisting of di- or monosubstituted
perylenes with all possible substituents, terrylene, quinacridone,
anthraquinone, nealred, titanylphthalocyanine, porphines and
porphyrines and derivatives thereof, polyfluorenes and derivatives
thereof and azo-dyes.
38. The hybrid solar cell according to claim 21, wherein a dye
layer is deposited in a thickness of about 5 to about 65 nm and the
SOL is deposited in a thickness of about 5 to about 50 nm.
39. The hybrid solar cell according to claim 21, wherein said cell
comprises more than one dye.
Description
[0001] The present invention is related to the manufacture of
organic hybrid solar cells in which the semiconductive oxide layer
of the organic hybrid cell is vapour deposited.
[0002] Among chief materials used in the past for solar cells have
been inorganic semiconductors made from, for example, silicon.
However, such devices have proven to be very expensive to
construct, due to the melt and other processing techniques
necessary to fabricate the semiconductor layer.
[0003] In an effort to reduce the cost of solar cells, organic
photoconductors and semiconductors have been considered, due to
their inexpensive formation by, e.g. thermal evaporation, spin
coating, self-assembly, screen printing, spray pyrolysis,
lamination and solvent coating. The most often followed strategies
in this field can be summarised as follows:
[0004] All-organic solar cells produced by vapour deposition are
known in the literature. For example, Tang (Tang, Two-layer organic
photovoltaic cell, Appl. Phys. Lett. 48(2) (1986) 183-5) reported
about organic thin two layer solar cells showing the following
structure: Substrate+ITO/CuPc (30 nm)/ST2 (50 nm)/Ag in which ITO
is indium tin oxide, CuPc is copper-phtalocyanine, ST2 is a dye and
in which all organic layers were deposited by evaporation. The
deposition by evaporation required source temperatures of about 500
and 600.degree. C., respectively, which the substrate was
maintained nominally at room temperature during deposition. The
resulting cell is herein designated as "Tang cell". The Tang cell
does not include an additional semiconducting oxide layer (SOL) and
has an efficiency of 0.96%.
[0005] Similarly, Wohrle et al. and Takahashi et al. reported about
organic two and three layer solar cells which were prepared by
vapour deposition and/or spin-coating (Wohrle D., Tennigkeit B.,
Elbe J., Kreienhoop L., Schnurpfeil G.: Various Porphyrins and
Aromatic Terracarbxcylic Acid Diimides in Thin Film p/n-Solar
cells, Molecular Crystals and Liquid Crystals 230 (1993B) 221-226
Takahashi, K.; Kuraya, N.; Yamaguchi, T.; Komura, T.; Murata, K.
Three-layer organic solar cell with high-power conversion
efficiency of 3.5%, Solar Energy Materials & Solar Cells 61
(2000) 403-416). These all organic cells do not contain an SOL
layer.
[0006] Petrisch and co-workers (Petrisch et al. Dye-based
donor/acceptor solar cells, Solar Energy Materials & Solar
Cells 61 (2000) 63-72) reported about organic solar cells
consisting of three dyes, in particular a perylene-tetracarboxylic
acid-bis imide with aliphatic side chains (perylene), a metal-free
phtalocyanine with aliphatic side chains (HPc). The materials are
soluble which allowed cell performance other than vapour depoition
(Yu G., Gao J., Hummelen J. C., Wudl F., Heeger A. J.: Polymer
Photovoltaic Cells: Enhanced Efficiencies via a network of Internal
Donor-Acceptor Heterojunctions, Science 270 (1995) 1789-1791.).
[0007] Further, laminated cells or cells containing mixtures of
donor and acceptor materials (polymers) were also reported by
Friend et al. (Friend et al., Nature 397 (1999) 121; Granstrom et
al., Nature 395 (1998) 257-260) and Sariciftici et al. (Sariciftici
et al. Science 258 (1992) 1474). Schon et al. (Schon et al. Nature
403 (2000) 408-410) reported on the use of single crystals of
organic material as doped pentacene having an efficiency of up to
2.4%. Most of the organic solar cells showing a higher efficiency
use I.sub.2/I.sub.3 as a doping system, which is unstable with
time.
[0008] The use of porous nanocrystalline TiO.sub.2 layers in solar
cells is further known from WO 91/16719, EP-A-0 333 641 and WO
98/48433 as well as from other publications of Gratzel et al. (Bach
U., Lupo D., Comte P., Moser J. E., Weissortel F., Solbeck J.,
Spreitzer H., Gratzel M.: Solid state dye-sensitized porous
nanocrystalline TiO.sub.2 solar cells with high photon-to-electron
conversion efficiencies, Nature 395 (1998) 583-585. Bach U.,
Gratzel M., Salbeck J., Weissortel F., Lupo D.: Photovoltaic Cell,
Brian O'Regan and Michael Gratzel: A low cost, high-efficiency
solar cell based on de-sensitized colloidal TiO.sub.2 films, Nature
353, (1991) 737-740.) These cells have efficiencies between 0.74%
(for the solid state solar cells) and 7.1% (for the liquid hybrid
solar cell). Nevertheless, as pointed out by the authors
themselves, the liquid cells described in this publications are
difficult to produce and have a reduced longterm stability, whilst
the solid cells described have a low efficiency. Furthermore, the
porous nano-crystalline TiO.sub.2 layer preparation requires high
temperature sintering with temperatures of 450.degree. C.
[0009] U.S. Pat. No. 3,927,228 to Pulker describes a method of
depositing titanium dioxide layers by evaporation of a molten
titanium-oxygen phase. The method of producing TiO.sub.2 layers
comprises evaporating a molten titanium-oxygen having a composition
corresponding to a proportion of the number of oxygen atoms to the
number of titanium atoms of from 1.6 to 1.8, and condensing the
vapour on a layer support in the presence of oxygen. The use of
this method for the production of solar cells is not disclosed or
proposed.
[0010] Therefore, most organic/hybrid solar cells known so far show
either a low efficiency, a small longterm stability, or they are
not suitable to be transferred on flexible substrates. Further, it
is still difficult to produce hybrid organic solar cells on large
sized carrier substrates.
[0011] It is therefore an object of the present invention to
provide a solar cell which is both inexpensive to produce and
sufficiently efficient as to be useful in terrestrial
applications.
[0012] It is a related object of the invention to provide a method
for the production of a thin, high efficient hybrid solar cell,
which can be produced on flexible substrates.
[0013] This problem is solved by a method for the production of a
hybrid organic solar cell in which the semiconducting oxide layer
(SOL) is introduced by thermal deposition. Preferably, the SOL
layer is vapour deposited.
[0014] The addition of the additional SOL layer can be used to
improve the efficiency of known organic solar cells, e.g. the ones
as reported by Friend et al. (Friend et al., Nature 397 (1999) 121;
Granstrom et al., Nature 395 (1998) 257-260).
[0015] The problem of the invention is further solved by a method
for the production of a hybrid organic solar cell having the
general structure Substrate+EM/HTM/dye/SOL/EM, or
Substrate+EM/SOL/dye/HTM/EM, or Substrate+EM/HTM/SOL/EM, in
which
[0016] EM is the electrode material, selected from the group
comprising of a transparent conductive oxide (TCO) and metal, with
at least one of the EM layers of the cell being a TCO,
[0017] HTM is the hole transport material,
[0018] SOL is a semiconducting oxide layer,
[0019] "dye" means a suited dye, for example, derivatives of
perylenes,
[0020] and in which the SOL layer of the hybrid solar cell is
vapour deposited.
[0021] The additional layer of SOL enhances the electron transport
to the anode and therefore increases the efficiency of the hybrid
organic solar cell according to the invention in comparison with
all-organic thin layer solar cells, like the above-mentioned "Tang
cell". The method according to the invention provides a solar cell
which is both inexpensive to produce and sufficiently efficient as
to be promising in view of future terrestrial applications.
[0022] The problem of the invention is further solved by a method
for the production of a hybrid organic solar cell having the
general structure Substrate+EM/HTM/dye/SOL/EM, or
Substrate+EM/SOL/dye/HTM/EM, or Substrate+EM/HTM/SOL/EM, in which
at least one second layer of the hybrid organic solar cell in
addition to the SOL layer is applied by vapour deposition.
[0023] The multilayer strategy of the present invention is a
promising alternative to the expensive production of solar cells
based on single crystal and polycrystalline materials, and a new
alternative to the known strategies in the filed of organic solar
cells and hybrid solar cells. All other layers of the hybrid
organic solar cell can be applied by conventional techniques, e.g.
thermal evaporation, spin coating, self-assembly, screen printing,
spray pyrolysis, lamination, solvent coating, LB technique,
sputtering and others.
[0024] In a preferred method of the invention, an additional layer
of lithium fluoride can be deposited and/or vapour deposited close
to the EM interfaces either on one side or both sides. The
additional layer of lithium fluoride can have a thickness of
between about 0.1 .ANG. to about 50 .ANG..
[0025] In a further preferred method of the invention, the surfaces
of the interfaces of the layers are increased. In general,
interfaces can be increased by the following approaches, namely use
of structured ITO or other EM, co-evaporation of HTM and dye and/or
dye/TiO2 (also in addition to layers of the bare materials) and
co-evaporation of HTM and dopant (e-acceptor, e.g. fullerene).
[0026] In a further preferred method of the invention, the
substrate is selected from glass, coated glass, polymeric foils,
like foils made from PET, PEN or PI (polyimide), norbornene-based
foils, SnO.sub.2-coated metal foils, e.g. stainless steel foils.
Preferably, the substrate is flexible.
[0027] In a further preferred method according to the invention EM
is selected from the group of indium tin oxide, fluorine doped tin
oxide, zinc oxide or doped zinc oxide. Further, in case of a metal,
the EM layer can be selected from Au, Al, Ca or Mg or combinations
of metals like Al/Li, Mg/Ag and the like. In order to allow a
proper function of the solar cell according to the invention, at
least one of the EM-layer(s) has to be transparent.
[0028] Most preferred is a method, in which EM is indium tin
oxide.
[0029] According to the invention, HTM can be selected from the
group of phthalocyanine and derivatives thereof (with or without a
central atom or group of atoms), metal-free and metal containing
porphyrins and derivatives thereof, TPD derivatives, triphenylamine
and its derivatives, (including different ground structure as
TDATAs, TTABs, TDABs, and cyclic variations like N-carbazoles and
its derivatives), thiophenes, polythiophenes and derivatives
thereof, polyanilines and derivatives thereof and hexabenzocoronene
and its derivatives, triphenyldiamine derivatives, aromatic diamine
compounds having connected tertiary aromatic amine units of
1,-bis(4-(di-p-tolylamino)phenyl)-cyclohexane, aromatic diamines
containing two or more tertiary amines and having two or more fused
aromatic rings substituted on the nitrogen atoms as typified by
4,4-bis[(N-1-naphthyl)-N-phenylamino]-biphenyl, aromatic trimers
having a starburst structure derived from triphenylbenzene,
aromatic diamines such as
N,N'-diphenyl-N,N'-bis(3-methyphenyl)-(1,1'-biphenyl)-4,4'diamine,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethyl-.alpha.,
,.alpha.'-bis(4-di-p-tolylaminophenyl)-p-xylene, triphenylamine
derivatives whose molecule is sterically asymmetric as a whole,
compounds having a plurality of aromatic diamino groups substituted
on a pyrenyl group, aromatic diamines having tertiary amine units
connected through an ethylene group, aromatic diamines having a
styryl structure, starbtirst type aromatic triamines, benzyl-phenyl
compounds, compounds having tertiary amine units connected through
a fluorene group, triamine compounds, bisdipyridylaminobiophenyl
compounds, N,N,N-triphenylamine derivatives, aromatic diamines
having a phenoxazine structure, diaminophenylanthridine, and other
carbazole derivatives, hydrazoen compounds, silazane compounds,
silanamine derivatives, phosphamine derivatives, quinacridone
compounds, stilbene compounds such as 4-di-p-tolylamino-stilbene
and 4-(di-p-tolylamino)-4'-[4-di-p-tolylamino)-styryl]stilbene,
triazole derivatives, oxadiazole derivatives, imidazole
derivatives, polyarylalkane derivatives, pyrazoline derivatives,
pyrazolone derivatives, oxadiazole derivatives, imidazole
derivatives, polyarylalkane derivatives, pyrazoline derivatives,
amino-substituted chalcone derivatives, oxazole derivatives,
styrylanthracene derivatives, fluorenone derivatives and polysilane
derivatives, all compounds alone or in admixture of two or more,
polymers, like polyvinyl carbazole and polysilanes,
polyphosphazenes, polyamides, polyvinyl triphenylamine, polymers
having a triphenylamine skeleton, polymers having triphenylamine
units connected through a methylene group and polymethacrylates
containing aromatic amine, preferably having an average molecular
weight of at least 1,000, more preferably at least -5,000. In
general, all kinds of hole transport materials known to the person
skilled in the art.
[0030] In an even more preferred method according to the invention,
HTM is copper-phthalocyanine (CuPc).
[0031] The substance of the SOL layer can be selected from the
group of all kinds of semiconducting oxides, like TiO.sub.2,
SnO.sub.2, ZnO, Sb.sub.2O.sub.3, and PbO.
[0032] Most preferred is TiO.sub.2.
[0033] In a further preferred method of the invention, the dye is
selected from the group of di- or monosubstituted perylenes with
all possible substituents, e.g. perylene anhydrid, perylene
dianhydrides, perylene imides, perylene diimides, perylene
imidazoles, perylene diimidazoles and derivatives thereof,
terrylene, quinacridone, anthraquinone, nealred,
titanylphthalocyanine, porphines and porphyrines and derivatives
thereof, polyfluorenes and derivatives thereof and azo-dyes. In
general, all suited and commercially available dyes which are known
to the person skilled in the art can be used.
[0034] Preferably, the dye layer is deposited in a thickness of
about 5 to about 65 nm and the SOL layer is deposited in a
thickness of about 5 to about 50 nm. More than one dye can be used
in one cell, which can be either applied by a layer-by-layer
technique or a co-evaporation of different dyes. The application of
several dyes leads to an advantageous broadening of the spectral
region in which the absorption takes places.
[0035] In a further preferred method according to the invention,
the substance of the HTM is doped. Possible approaches for doping
can be employed by mixing the material of the HTM layer prior to
application with, for example, Tris(4-bromophenyl)ammoniumyl
hexachworoantimonate (N(PhBr).sub.3SbCl.sub.6),
2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F.sub.4-TCNQ)
or Nitrosonium-tetrafluorborat (BF.sub.4NO). Co-evaporation of
dopants like 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane
(F.sub.4-TCNQ) or other electron acceptors is also possible. The
dopants can be used in combination with Li-salts, e.g.
Bistrifluoromethane sulfonimide Li-salt
(Li((CF.sub.3SO.sub.2).sub.2N)). The dopants can be used in both
fully or non-fully evaporated cells.
[0036] The problem of the present invention is further solved by a
hybrid solar cell which is obtainable by the inventive method,
mentioned above.
[0037] Preferably the thickness of the complete cell is about 100
nm, and the hybrid solar cell has an efficiency of about 0.7 to
about 1.3% at 60 mW/cm.sup.2.
[0038] Most preferred is a hybrid solar cell according to the
invention, which is flexible.
[0039] The term "hybrid" is generally known in chemistry as
combination of organic and inorganic materials forming any kind of
new structure. In the case of photovoltaic cells this term has been
introduced for the first time by Hagen et al. (J. Hagen, W.
Schaffrath, P. Otschik, R. Fink, A. Bacher, H.-W. Schmidt, L D.
Haarer, Synth. Met., 89, 215 (1997).) for describing a dye
sensitized solid state solar cell using nanocrystalline TiO.sub.2
and TPD derivatives as HTM. Within the invention, the term "thin
film hybrid photovoltaic cell" may be used in order to indicate the
difference between dye sensitized solar cells with porous
nanocrystalline TiO.sub.2 and the inventive solar cells with a
vapour deposited TiO.sub.2 layer.
[0040] In general, the inventors developed a new concept to
fabricate hybrid organic solar cells. The new idea in this concept
is that a SOL layer was introduced into the cell by vapour
deposition. All other layers of the hybrid organic solar cell can
be applied by conventional techniques, e.g. thermal evaporation,
spin coating, self-assembly, screen printing, spray pyrolysis,
lamination, solvent coating, LB technique, sputtering and others.
In one embodiment of the invention, all layers, or all layers
except one or both EM layer(s) are vapour deposited. Compared to
the fully organic solar cells consisting of derivatives of
phthalocyanin and perylene, an additional layer of TiO.sub.2 was
introduced. This surprisingly enhances the electron transport to
the anode. The resulting cell shows, in one example a configuration
of the following structure: Substrate+ITO/HTM/dye/TiO.sub.2/Al,
with a total thickness<100 nm.
[0041] The advantages of this concept are the low costs, use of
purchasable materials with high thermal and electrochemical
stability. Furthermore the possibility to prepare large area
photo-voltaic cells is given and no further temperature treatment
is needed, which enables the application to flexible
substrates.
[0042] To determine the best cell performance, we used the
combinatorial method for vapor deposition by varying the TiO.sub.2
layer thickness, the CuPc layer thickness, and the thickness of the
dye derivatives. Cells were characterized by measuring I-V
characteristics of solar cells. The use of TiO.sub.2 improved the
energy conversion efficiency of solar cells from 0.7 to 1.3% (light
of 60 mW/cm.sup.2). Further, co-vapor deposition of TiO.sub.2 and
dye or a modified device structure ITO/TiO.sub.2/dye/HTM/Au are
possible.
[0043] The method according to the present invention shall now be
further explained with reference to the figures in which
[0044] FIG. 1 shows a schematic outline of the composition of
different hybrid solar cell prepared according to the
invention,
[0045] FIG. 2 shows a schematic outline of the preparation of a
layer thickness gradient,
[0046] FIG. 3 shows a schematic outline of the preparation of a
hybrid solar cell prepared according to the invention, in which a
cell was produced having a TiO.sub.2 gradient, in which the
substrate/EM carrier is schematically shown at (1), the HTM layer
at (2), the substrate/EM/HTM carrier at (3), the dye layer at (4),
the substrate/EM/HTM/dye carrier at (5), the mask at (6) and the
TiO.sub.2 gradient layer at (7),
[0047] FIG. 4 shows an SEM of a cross section of a cell produced
according to the invention showing the structure Substrate (1)+EM
(2)/HTM (3)+dye (4)/SOL (5)/EM (6),
[0048] FIG. 5 shows the current-voltage curves of hybrid organic
solar cells with different TiO.sub.2 layer thickness, and
[0049] FIG. 6 shows current-voltage curves showing the light
intensity dependence of I.sub.sc and V.sub.oc of a hybrid organic
solar cell according to the invention.
EXAMPLE 1
Preparation of a Cell According to the Invention
[0050] In a first step according to FIG. 3, commercially available
EM coated glass (1) is used as starting material . Suited EM
materials are all materials which can be used to create transparent
electrodes, like indium tin oxide, fluorine doped tin oxide, zinc
oxide or doped zinc oxide. Further, an evaporated metal electrode
(EM layer) selected from metals, like Au, Al, Ca or Mg, or
combinations of metals like Al/Li, Mg/Ag, and the like can be used.
In order to allow a proper function of the solar cell according to
the invention, at least one of the EM-layers should be a TCO.
[0051] The starting material is then coated with a constant
thickness layer of HTM (2), which can be applied by vapour
deposition, resulting in a HTM-coated device substrate/TCO/HTM (3).
Suitable HTM materials can be selected from the group of
phthalocyanine and derivatives thereof (with or without a central
atom or group of atoms), metal-free and metal containing porphyrins
and derivatives thereof, TPD derivatives, triphenylamine and its
derivatives, (including different ground structure as TDATAs,
TTABs, TDABs, and cyclic variations like N-carbazoles and its
derivatives), thiophenes, polythiophenes and derivatives thereof,
polyanilines and derivatives thereof and hexabenzocoronene and its
derivatives. In general, all kinds of hole transport materials
known to the person skilled in the art can be used.
[0052] For example, CuPc or its derivatives can be used having the
following formula: ##STR1##
[0053] Further suited hole transporting agents are in principle
disclosed in European patent application EP 00 111 493.3 [not yet
published] and EP 0 901 175 A2, whose disclosures are incorporated
herein by reference.
[0054] More particularly, EP 0 901 175 A2 discloses suited organic
hole conducting agents which include aromatic diamine compounds
having connected tertiary aromatic amine units of
1,-bis(4-(di-p-tolylamino)phenyl)-cyclohexane as described in JP-A
194393/1984, aromatic diamines containing two or more tertiary
amines and having two or more fused aromatic rings substituted on
the nitrogen atoms as typified by
4,4-bis[(N-1-naphthyl)-N-phenylamino]-biphenyl as described in JP-A
234681/1983, aromatic trimers having a starburst structure derived
from triphenylbenzene as described in U.S. Pat. No. 4,923,774,
aromatic diamines such as
NN'-diphenyl-N,N'-bis(3-methyphenyl)-(1,1'-biphenyl)-4,4'diamine as
described in U.S. Pat. No. 4,764,625,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethyl-.alpha.,.alpha.'-bis(4-di-p-
-tolylaminophenyl)-p-xylene as described in JP-A269084/1991,
triphenylamine derivatives whose molecule is sterically asymmetric
as a whole as described in JP-A 129271/1992, compounds having a
plurality of aromatic diamino groups substituted on a pyrenyl group
as described in JP-A 175395/1992, aromatic diamines having tertiary
amine units connected through an ethylene group as described in
JP-A 264189/1992, aromatic diamines having a styryl structure as
described in JP-A 290851/1992, starburst type aromatic triamines as
described in JP-A 308688/1992, benzyl-phenyl compounds as described
in JP-A 364153/1992, compounds having tertiary amine units
connected through a fluorene group as described in JP-A 25473/1993,
triamine compounds as described in JP-A 239455/1993,
bisdipyridylaminobiophenyl compounds as described in JP-A
320634/1993, N,N,N-triphenylamine derivatives as described in JP-A
1972/1994, aromatic diamines having a phenoxazine structure as
described in JP-A 290728/1993, diaminophenylanthridine derivatives
as described in JP-A 45669/1994, and other carbazole
derivatives.
[0055] Other hole transporting agents which are disclosed in EP 0
901 175 and which may be used in the present invention, include
hydrazoen compounds (JP-A 311591/1990), silazane compounds (U.S.
Pat. No. 4,950,950), silanamine derivatives (JP-A 49079/1994),
phosphamine derivatives (JP-A 25659/1994), quinacridone compounds,
stilbene compounds such as 4-di-p-tolylamino-stilbene and
4-(di-p-tolylamino)-4'-[4-di-p-tolylamino)-styryl]stilbene,
triazole derivatives, oxadiazole derivatives, imidazole
derivatives, polyarylalkane derivatives, pyrazoline derivatives,
pyrazolone derivatives, oxadiazole derivatives, imidazole
derivatives, polyarylalkane derivatives, pyrazoline derivatives,
amino-substituted chalcone derivatives, oxazole derivatives,
styrylanthracene derivatives, fluorenone derivatives and polysilane
derivatives. These compounds may be used alone or in admixture of
two or more. The same applies also to the other compounds disclosed
herein, including those incorporated herein by reference.
[0056] In addition to the aforementioned compounds, polymers can be
used as the hole transporting agent. Suitable polymers include
polyvinyl carbazole and polysilanes (Appl. Phys. Lett., vol. 59,
2760, 1991), polyphosphazenes (JP-A 310949/1993), polyamides (JP-A
10949/1993), polyvinyl triphenylamine (Japanese Patent Application
No. 133065(1993), polymers having a triphenylamine skeleton (JP-A
133065/1992), polymers having triphenylamine units connected
through a methylene group (Synthetic Metals, vol 55-57, 4163, 1993)
and polymethacrylates containing aromatic amine (J. Polym. Sci.,
Polym. Chem. Ed., vol 21, 969, 1983). When polymers or mixtures
thereof are used as the hole transporting agent, they preferably
have a number average molecular weight of at least 1,000, more
preferably at least -5,000.
[0057] In a second step according to FIG. 3, constant thickness
layers of a dye (4) are vapour deposited on the substrate/EM/HTM
carrier (3), in this case dyes named STI1/1
(N,N'-dimethyl-3,4:9,10-perylene-bis(carboximid) or ST2
(Bisbenzimidazol[2,2-a:1',2'-b']anthra[2,1,9-def:6,5,10-d'e'f']diisoquino-
line-6,11-dione) (both commercially available from Syntec Company)
are used. In our experiments, we tested the different dyes in a
layer thickness in the range from 5 to 50 nm. In general, suited
dyes are, for example, di- or mono-substituted perylenes with all
possible substituents. For the structure of dyes, all types of
perylene diimides with different amino residues and all types of
perylene benzimidazoles with different diamine components can be
added. Moreover, the perylene rest can be differently
substituted.
[0058] The general structure of perylene diimidazole is shown in
the following formula ##STR2## in which R.sub.1, R.sub.2, R.sub.3
are alkyl, aryl alkoxyl or halogen, etc.
[0059] The general structure of perylene diimide is shown in the
following formula ##STR3## in which R.sub.1, R.sub.2, R.sub.3 are
alkyl, aryl, alkoxyl, or halogen, etc.
[0060] The inorganic oxide layer or electrode transport layer can
consist of all kinds of semi-conducting oxides as TiO.sub.2,
SnO.sub.2, ZnO, Sb.sub.2O.sub.3, PbO, etc.
[0061] In a third step according to FIG. 3, in this embodiment a
step gradient of titanium dioxide (7) is evaporated on the
substrate/EM/HTM/dye carrier (5) using a mask (6). In addition to
the variation of the titanium dioxide layer described for this
embodiment, similar strategies can be used in order to produce
other embodiments with gradients for all materials possible to be
used as EM, HTM, dye or SOL. Titanium dioxide was evaporated from a
tantalum crucible starting with Ti.sub.3O.sub.5 powder (pellets
commercially available from Balzers); the vacuum chamber was
evacuated to a pressure of 2.0.times.10.sup.-5 mbar followed by
feeding O.sub.2 into the vacuum deposition chamber via a needle
valve resulting in an O.sub.2 partial pressure of
2.5.times.10.sup.-4 mbar (possible partial pressures are in the
range of 2.0.times.10.sup.-5 to 3.0.times.10.sup.-4 mbar). The
crucible--substrate distance was 36 cm. The evaporation rates were
controlled to be in the range between 0.11 to 0.5 nm/s. The
evaporation rates were detected with oscillating quartz crystals
placed inside the evaporation chamber. The production of the
gradient is also schematically depicted in FIG. 2.
[0062] Finally, 24 Al stripes were applied as electrodes on top of
the resulting hybrid organic solar cells having (in this
embodiment) the structure: Substrate+ITO/CuPc (35 nm)/ST2 (25
nm)/TiO.sub.2(0, 15 or 35 nm)/Al
[0063] FIG. 4 shows an SEM of a cross section of the cell produced
according to the invention in which the substrate is glass (1) on
which a layer of ITO (2), a layer of both CuPc (35 nm, (3)) and ST2
(25 nm (4)), a layer of TiO.sub.2 (5) and a layer of Al (6) is
applied.
EXAMPLE 2
Characteristics of a Cell Prepared According to the Invention
[0064] The hybrid organic solar cell produced according to example
1 was tested for its current-voltage characteristics and light
intensity dependence of I.sub.sc and V.sub.oc. An Oriel 75W xenon
short arc lamp with a water filter, a 345 nm sharp edge filter, a
mirror and a PP diffuser was used as the light source.
Current-voltage characteristics were measured with an SMU Keithley
2400, an IEEE-card together with a self-developed Labview measuring
program (I [A], V [V], I.sub.dens [mA/cm.sup.2], FF [%], P.sub.max
[mW/cm.sup.2], .eta. [%]. Standard measurement parameters were:
ambient conditions, 60 mW/cm.sup.2 to 100 mW/cm.sup.2, a cycle of 0
V to -0.1 V to +1.0 V (illuminated and dark), a 5 mA step size and
3 seconds delay time. The results of the measurements are
graphically depicted in FIGS. 5 and 6 and listed in Tables 1 and 2,
below. TABLE-US-00001 TABLE 1 Current-voltage characteristics
Device I.sub.sc [mA/cm.sup.2] V.sub.oc [mV] FF [%] .eta. [%] A (0
nm TiO.sub.2) 1.861 420 57.6 0.75 B (15 nm TiO.sub.2) 2.816 440
42.5 0.87 C (35 nm TiO.sub.2) 3.326 440 42.4 1.04
[0065] The results show, that the introduction of a vapor-deposited
layer of TiO.sub.2 clearly increases the efficiency of the hybrid
solar cell up to a value of .eta.>1%. TABLE-US-00002 TABLE 2
Light intensity dependence of I.sub.sc and V.sub.oc for device C
(35 nm TiO.sub.2) Light Int. [mW/cm.sup.2] I.sub.sc [mA/cm.sup.2]
V.sub.oc [mV] FF [%] .eta. [%] 7 0.280 375 52.3 0.79 11 0.438 385
53.4 0.82 22 1.101 415 51.7 1.07 39 2.008 435 49.9 1.12 60 3.572
445 49.1 1.30 82 5.319 455 47.3 1.40
[0066] The results show a value of .eta.=1.30% at 60 mW/cm.sup.2,
indicating the good efficiency of the inventive hybrid organic
solar cell.
* * * * *