JP5542900B2 - Photovoltaic devices containing semiconductor nanocrystals - Google Patents

Description

  The present invention relates to photovoltaic devices comprising semiconductor nanocrystals.

(Research or development funded by the federal government)
The US federal government, in accordance with grant number 6897284 of the Soldier Nanotechnology Institute,
You may have certain rights in the invention.

A photovoltaic device can generate a current in response to excitation of the active component of the device. Excitation can be stimulated by illuminating the device with the appropriate wavelength of light, while simultaneously applying a voltage across the device. The absorbent component can be a polymer such as a conjugated organic polymer or a polymer comprising a layer of absorbent moieties or organic molecules. The wavelength response profile and other physical properties of the device can be altered by the electronic structure (eg, energy gap) of the materials used.

(Summary)
In general, a photovoltaic device can include a plurality of semiconductor nanocrystals. The semiconductor nanocrystals can be inorganic semiconductor particles, for example 1-15 nm in diameter, optionally decorated with a layer of organic ligands. Nanocrystals can exhibit a strong quantum confinement effect, a bottom-up chemical approach for the creation of composite heterostructures with electronic and optical properties that can be tuned by the size and composition of the nanocrystal Can be used when designing.

Semiconductor nanocrystals can be used as an absorptive material for photovoltaic devices.
Semiconductor nanocrystals can be dispersed in a liquid and are therefore compatible with thin film deposition techniques such as rotational molding, drop casting, and dip coating. However, bulk semiconductor nanocrystal solids resulting from these deposition techniques have poor electrical transport properties in solid phase devices. Rather than bulk solids, layers such as thin films of semiconductor nanocrystals (eg, a single layer or multiple layers) can be used in photovoltaic devices. The monolayer provides the beneficial light absorption properties of semiconductor nanocrystals while minimizing the impact on electrical performance.

Devices that use organic materials in the hole transport layer and / or electron transport layer (or both) can have high efficiency conversion from electricity to light, but have a short lifetime due to the inherent instability of the organic material. Can be. As demonstrated by photoluminescence studies, inorganic nanocrystals themselves can be inherently more stable than their organic counterparts. Devices that utilize semiconductor nanocrystals for absorption and inorganic semiconductors for electrical transport can achieve excellent optoelectronic performance and long-term stability. The inorganic semiconductor can be deposited by a low temperature method such as sputtering, vacuum evaporation, ink jet printing, or ion plating.

Semiconductor nanocrystals can be deposited on the substrate using microcontact printing.
Advantageously, microcontact printing is performed on a surface on a micron scale or nanoscale (eg, less than 1 mm, less than 500 μm, less than 200 μm, less than 100 μm,
Patterning of less than 25 μm or less than 1 μm). In particular, a single layer of semiconductor nanocrystals can be deposited by microcontact printing. This approach allows for a substantially dry (ie, substantially solvent free) application of the patterned semiconductor nanocrystal coating to the substrate. Therefore, a wide variety of substrates can be used. This is because the choice of substrate is not constrained by solubility and surface chemistry requirements.

In one aspect, the photovoltaic device comprises a first charge transport layer containing a first inorganic material in contact with a first electrode disposed to introduce charge into the first charge transport layer, a second charge transport. A second charge transport layer in contact with a second electrode disposed to introduce charge into the layer, and a plurality of semiconductor nanostructures disposed between the first charge transport layer and the second charge transport layer Includes crystals.

The first inorganic material can be amorphous or polycrystalline. The first inorganic material can be an inorganic semiconductor. The inorganic semiconductor can include a metal chalcogenide. The metal chalcogenide can be a mixed metal chalcogenide. The metal chalcogenide can include zinc oxide, titanium oxide, niobium oxide, zinc sulfide, indium tin oxide, or mixtures thereof.

The second charge transport layer can include a second inorganic material. The second inorganic material can be amorphous or polycrystalline. The second inorganic material can be an inorganic semiconductor. The inorganic semiconductor can include a metal chalcogenide. The metal chalcogenide is
It can be a mixed metal chalcogenide. The metal chalcogenide can include zinc oxide, titanium oxide, niobium oxide, zinc sulfide, indium tin oxide, or mixtures thereof.

The first charge transport layer can be a hole transport layer or an electron transport layer. The plurality of semiconductor nanocrystals can form a single layer. The plurality of semiconductor nanocrystals are:
It can be a substantially monodisperse population of semiconductor nanocrystals. The device can be transparent. The second electrode can be in direct contact with the plurality of semiconductor nanocrystals.

The plurality of semiconductor nanocrystals can form a layer having a thickness of 4 nm to 2000 nm. The layer can have a thickness of less than 100 nm.

In another aspect, a method for manufacturing a device includes depositing a first charge transport layer comprising a first inorganic material on an electrode, and depositing a plurality of semiconductor nanocrystals on the electrode (where the plurality The semiconductor nanocrystal is electrically contacted with the first charge transport layer) and depositing a second charge transport layer comprising a second inorganic material on the electrode, wherein the plurality of semiconductor nanocrystals In electrical contact with the second charge transport layer.

Depositing the first inorganic material can include sputtering. Depositing the second inorganic material can include sputtering.

In another aspect, a method of generating an electric current includes exposing the device to light of an excitation wavelength, wherein the device is in contact with a first electrode arranged to introduce charge into the first charge transport layer. A first charge transport layer containing a first inorganic substance, a second charge transport layer in contact with a second electrode arranged to introduce charge into the second charge transport layer, and the first charge transport layer And a plurality of semiconductor nanocrystals disposed between the second charge transport layer.

Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.

FIG. 1 is a schematic diagram illustrating a photovoltaic device. FIG. 2 is a diagram illustrating a method of forming a photovoltaic device. 3A-3E are schematic diagrams illustrating photovoltaic devices. FIG. 4 is a graph showing optical and electrical characteristics of the photovoltaic device.

(Detailed explanation)
A photovoltaic device can include two layers that separate the two electrodes of the device. The material of one layer can be selected based on the ability of the material to transport holes, ie a hole transport layer (HTL). The material of the other layer can be selected based on the ability of the material to transport electrons, ie it can be an electron transport layer (ETL).
Usually, the electron transport layer includes an absorptive layer. When a voltage is applied and the device is illuminated, one electrode accepts holes (positive charge carriers) from the hole transport layer and the other electrode accepts electrons from the electron transport layer. Holes and electrons are generated as excitons in the absorbing material. The device can include an absorbent layer between the HTL and the ETL. The absorption layer can include materials selected for its absorption characteristics, such as absorption wavelength or line width.

The photovoltaic device can have a structure as shown in FIG. 1 and includes a first electrode 2, a first layer 3 in contact with the electrode 2, a second layer 4 in contact with the first layer 3, and And a second electrode 5 in contact with the second layer 4. The first layer 3 can be a hole transport layer, and the second layer 4 can be an electron transport layer. At least one layer can be non-polymeric. The layer can include an inorganic material. One of the electrodes having this structure is in contact with the substrate 1. Each electrode can be in contact with a power source to provide a voltage across the structure. When an appropriate polarity and magnitude of voltage is applied across the device, a photocurrent can be generated by the absorbing layer. The first layer 3 may comprise a plurality of semiconductor nanocrystals, for example a substantially monodispersed population of nanocrystals.

Alternatively, a separate absorbent layer (not shown in FIG. 1) can be included between the hole transport layer and the electron transport layer. The separate absorbent layer can include a plurality of nanocrystals. The layer comprising nanocrystals can be a single layer of nanocrystals or a multilayer of nanocrystals. In some cases, the nanocrystal-containing layer can be an incomplete layer, ie, a layer having a region that lacks material such that a layer adjacent to the nanocrystal layer can be in partial contact. The nanocrystal and the at least one electrode have a bandgap offset sufficient to transfer charge carriers from the nanocrystal to the first electrode or the second electrode. The charge carriers can be holes or electrons. Depending on the electrode's ability to transfer charge carriers, a light-induced current can flow in a manner that facilitates light detection.

A photovoltaic device comprising a semiconductor nanocrystal can be made by spin molding a solution comprising the HTL organic semiconductor molecule and the semiconductor nanocrystal, the HTL being under a semiconductor nanocrystal monolayer by phase separation. (See, eg, US Patent Application No. 10 / 400,907 and US Patent Application Publication No. 2004/0023010, filed March 28, 2003, each of which is incorporated by reference in its entirety). This phase separation technique is based on organic semiconductors HTL and E
A reproducible placement of a single layer of semiconductor nanocrystals between the TL, thereby efficiently utilizing the favorable light absorption properties of the semiconductor nanocrystals, along with minimizing their impact on electrical performance did. Devices made by this technique were limited by impurities in the solvent and the need to use organic semiconductor molecules that are soluble in the same solvent as the semiconductor nanocrystals. The phase separation technique was unsuitable for depositing monolayers of semiconductor nanocrystals on both HTL and HIL (since the solvent destroys the underlying organic film). Also,
Phase separation methods cannot control the position of semiconductor nanocrystals that emit different colors on the same substrate; similarly, phase separation methods can pattern nanocrystals that emit different colors on the same substrate. There wasn't.

Furthermore, the organic material used in the transport layer (ie, hole transport layer, hole injection layer, or electron transport layer) can be more unstable than the semiconductor nanocrystal used in the absorbent layer. As a result, the age of operation of the organic material limits the lifetime of the device. A long-life light-emitting device can be manufactured using a device using a long-life material for the transport layer.

The substrate can be opaque or transparent. Transparent devices can be manufactured using transparent substrates. See, for example, Bulovic, V. et al., Nature 1996, 380, 29; and Gu, G. et al., Appl. Phys. Lett. 1996, 68, 2606-2608. Each is incorporated by reference in its entirety. The substrate can be rigid or flexible. The substrate can be plastic, metal, or glass. The first electrode can be a high work function hole injection conductor, such as, for example, an indium tin oxide (ITO) layer. Other first electrode materials can include gallium indium tin oxide, zinc indium tin oxide, titanium nitride, or polyaniline. The second electrode is composed of an electron injection metal having a low work function (for example, less than 4.0 eV) such as Al, Ba, Yb, Ca, lithium aluminum alloy (Li: Al), or magnesium silver alloy (Mg: Ag). can do. The second electrode such as Mg: Ag
It can be coated with an opaque protective metal layer, for example a layer of Ag to protect the cathode layer from atmospheric oxidation, or a relatively thin layer of substantially transparent ITO. The first electrode can have a thickness of about 500 Angstroms to 4000 Angstroms. The first layer is about 5
It can have a thickness of 0 angstroms to about 5 micrometers, for example, a thickness in the range of 100 angstroms to 100 nm, 100 nm to 1 micrometer, or 1 micrometer to 5 micrometers. The second layer can have a thickness of about 50 angstroms to about 5 micrometers, such as a thickness in the range of 100 angstroms to 100 nm, 100 nm to 1 micrometer, or 1 micrometer to 5 micrometers. The second electrode can have a thickness from about 50 angstroms to greater than about 1000 angstroms.

The hole transport layer (HTL) or the electron transport layer (ETL) can contain an inorganic substance such as an inorganic semiconductor. The inorganic semiconductor can be any material having a band gap greater than the emission energy of the emitting material. Inorganic semiconductors include metal oxides, metal sulfides, metal selenides, metal tellurides, metal nitrides, metal phosphides, metal arsenides, or metal arsenides, metal chalcogenides, metal pnictides, or elements Semiconductors can be included. For example, the inorganic material can include: zinc oxide, titanium oxide, niobium oxide, indium tin oxide, copper oxide, nickel oxide, vanadium oxide, chromium oxide, indium oxide, tin oxide, gallium oxide, Manganese oxide, iron oxide, cobalt oxide, aluminum oxide, thallium oxide, silicon oxide, germanium oxide, lead oxide, zirconium oxide, molybdenum oxide, hafnium oxide, tantalum oxide, tungsten oxide, cadmium oxide, iridium oxide, rhodium oxide, ruthenium oxide , Osmium oxide, zinc sulfide, zinc selenide, zinc telluride, cadmium sulfide, cadmium selenide, cadmium telluride, mercury sulfide, mercury selenide, mercury telluride, silicon carbide, diamond (carbon),
Silicon, germanium, aluminum nitride, aluminum phosphide, aluminum arsenide, gallium nitride, gallium phosphide, gallium arsenide, gallium antimonide, indium nitride,
Indium phosphide, indium arsenide, indium antimonide, thallium nitride, thallium phosphide, thallium arsenide, thallium antimonide, lead sulfide, lead selenide, lead telluride, iron sulfide, indium selenide, indium sulfide, telluride Indium, gallium sulfide, gallium selenide, gallium telluride, tin selenide, tin telluride, tin sulfide, magnesium sulfide, magnesium selenide, magnesium telluride, or mixtures thereof. The metal oxide can be a mixed metal oxide such as ITO. On the device
A layer of pure metal oxide (ie, a metal oxide having a single substantially pure metal) can produce crystalline regions over time and reduce the performance of the device. Mixed metal oxides tend to reduce the formation of the crystalline region and can provide a device lifetime that is longer than that obtained with pure metal oxides. The metal oxide can be a doped metal oxide. Here, the doping may be, for example, oxygen deficiency, halogen dopant (haloge).
n dielectric) or mixed metals. The inorganic semiconductor can include a dopant. In general, the dopant can be a p-type or n-type dopant. The HTL can include a p-type dopant, while the ETL can include an n-type dopant.

Single crystal inorganic semiconductors have been proposed for charge transport to the semiconductor nanocrystals of the device. Single crystal inorganic semiconductors are deposited by techniques that require heating the substrate to be coated to a high temperature. However, the upper semiconductor must be deposited directly on the nanocrystal layer. This is not robust to high temperature processing and is not suitable for easy epitaxial growth. Also, epitaxial techniques (such as chemical vapor deposition) are costly to manufacture and generally cannot be used to coat large areas (i.e., areas larger than 12 inch (30.48 cm) diameter wafers).

Advantageously, the inorganic semiconductor can be deposited on the substrate at a low temperature, for example by sputtering. Sputtering is performed by applying a high voltage to a low-pressure gas (for example, argon) to create a plasma of electrons and gas ions in a high energy state. The plasma ions to which the voltage is applied hit the desired coating material of the target, eject atoms from the target with sufficient energy, move to the substrate, and bond.

The substrate or device to be manufactured is cooled or heated for temperature control during the growth process. The temperature affects the crystallinity of the deposited material and how much it interacts with the surface being deposited. The deposited material can be polycrystalline or amorphous.
The deposited material may have a crystalline domain with a size in the range of 10 angstroms to 1 micrometer. By changing the gas or gas mixture used for the sputtering plasma, the doping concentration can be controlled. The nature and degree of doping affects the conductivity of the deposited film and its stability to optically quench adjacent excitons. By growing one substance on top of another, pn, or p
-I-n diodes can be made. The device can be optimized to transport charge to the semiconductor nanocrystal monolayer.

Applying the layer on one surface of the electrode by spin coating, dip coating, vapor deposition,
It can be deposited by sputtering or other thin layer deposition methods. The second electrode can be sandwiched, sputtered or deposited on the exposed surface of the solid layer. One or both of the electrodes can be patterned. The electrode of the device can be connected to a voltage source by a conductive path. Light is generated from the device when a voltage is applied.

Microcontact printing provides a method for applying a material to a predefined area on a substrate.
A predefined area is an area on a substrate to which the substance is selectively applied. The substance and substrate are
The material can be selected to remain substantially completely within the predefined area. By selecting a predefined region that forms a pattern, the material can be applied to the substrate such that the material forms a pattern. The pattern can be a regular pattern (such as an array or a series of lines) or an irregular pattern. When the pattern of the material is formed on the substrate, the substrate may have a region containing the material (predefined region) and a region substantially free of the material. In some situations, the material forms a monolayer on the substrate. The predefined area can be a discontinuous area. That is, when a substance is applied to a predefined area of the substrate, a location containing the substance can be separated by another location that is substantially free of the substance.

In general, microcontact printing begins with the formation of a pattern mold. The mold has a surface having a pattern of ridges and depressions. For example, by coating the pattern surface of the mold with a liquid polymer precursor that is cured while in contact with the pattern mold surface, a stamp having a complementary pattern of ridges and depressions is formed. The stamp can then be inked. That is, the stamp is contacted with the material to be deposited on the substrate. The material is reversibly adhered to the stamp. The inked stamp is then contacted with the substrate. The raised area of the stamp can contact the substrate and the recessed area of the stamp can be separated from the substrate. When the inked stamp contacts the substrate, the ink material (or at least a portion thereof) is transferred from the stamp to the substrate. In this manner, the pattern of the raised portion and the recessed portion is transferred from the stamp to the substrate as a region containing the substance and a region not containing the substance on the substrate. Microcontact printing and related techniques are described, for example, in US Pat. Nos. 5,512,131, 6,180,239, and 6,518,168, each of which is incorporated by reference in its entirety. In some cases, the stamp may be a featureless stamp having an ink pattern. Here, the pattern is formed when the ink is applied to the stamp. The whole is incorporated by citation,
See US patent application Ser. No. 11 / 253,612, filed Oct. 21, 2005. In addition, the ink can be treated (eg, chemically or thermally) prior to transferring the ink from the stamp to the substrate. In this way, the patterned ink can be exposed to a state that is not compatible with the substrate.

FIG. 2 shows a flowchart outlining the basic steps in the microcontact printing process. First, a silicon master is created using standard semiconductor processing techniques that define patterns on the silicon surface, such as ridge and depression patterns (alternatively, in the case of patternless deposition, A blank Si master can be used). A polydimethylsiloxane (PDMS, eg Sylgard 184) precursor is then mixed, degassed, poured onto the master, degassed again, and room temperature (or higher than room temperature for faster cure times) (Step 1). The PDMS stamp with the surface containing the silicon master pattern is then removed from the master and cut to the desired shape and size. Then
This stamp is coated with a surface chemical layer. This is selected so that the ink can be easily adhered and released as needed. For example, the surface chemical layer can be a chemical vapor deposited perylene-C layer. The surface chemical layer can be, for example, 0.1-2 μm thick and depends on the pattern to be replicated (step 2). Next, ink is applied to the stamp by, for example, rotational molding, syringe pump dispensing, or ink jet printing of the semiconductor nanocrystal solution (step 3). This solution is, for example,
It can have a concentration of 1-10 mg / mL in chloroform. The concentration can be varied depending on the desired outcome. The inked stamp can then be brought into contact with the substrate and gentle pressure applied, for example for 30 seconds, to completely transfer the ink (ie, semiconductor nanocrystal monolayer) to the new substrate (step 4). 2A and 2B show a specimen of an ITO coated glass substrate. Hole transport and / or hole injection layer containing organic semiconductor (each H
TL and HIL) are thermally deposited on the ITO substrate. The patterned semiconductor nanocrystal monolayer is transferred to this HTL layer and then the rest of the device (optionally, eg, electron transport layer (ETL), electron injection layer (EIL), and metal contact) is added. (Step 5). For example, U.S. Patent Application No. 11/2, both filed on October 21, 2005.
See 53,595 and 11 / 253,612, and 11 / 032,163, filed January 11, 2005. Each of these is incorporated by reference in its entirety.

When nanocrystals absorb photons, excited electron-hole pairs are generated. The absorption wavelength is
Related to the effective band gap of quantum confined semiconductor materials. The band gap is a function of nanocrystal size, shape, material, and arrangement. Nanocrystals with small diameters can have intermediate properties between molecules and bulk form materials. For example, nanocrystals based on semiconductor materials with small diameters can exhibit both electron and hole quantum confinement in all three dimensions, increasing the effective band gap of the material with decreasing crystal size. . Therefore, as the crystal size decreases, both the absorption and emission of the nanocrystal shift to blue, ie higher energy.

Semiconductors that form nanocrystals include II-VI group compounds, II-V group compounds,
Group III-VI compounds, Group III-V compounds, Group IV-VI compounds, I-III-
Group VI compounds, II-IV-VI compounds, or II-IV-V compounds such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, MgO,
MgS, MgSe, MgTe, HgO, HgS, HgSe, HgTe, AlN, AlP,
AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs
, InSb, TlN, TlP, TlAs, TlSb, PbS, PbSe, PbTe, or mixtures thereof.

A method for preparing monodisperse semiconductor nanocrystals involves pyrolysis of an organometallic reagent such as dimethylcadmium that is injected into a hot coordinating solvent. This allows for discrete nucleation and results in controlled growth of macroscopic nanocrystals. The preparation and manipulation of nanocrystals is described, for example, in US Pat. Nos. 6,322,901 and 6,576,291, and US Patent Application No. 60 / 550,314, which are incorporated by reference in their entirety. The method for producing nanocrystals is a colloidal growth process. Colloidal growth occurs by rapidly injecting M and X donors into a hot coordinating solvent. This implantation produces nuclei that can be grown in a controlled manner to form nanocrystals. The reaction mixture can be heated gently to grow and anneal the nanocrystals. Both the average size and the size distribution of the nanocrystals in the sample depend on the growth temperature. The growth temperature required to maintain stable growth increases with increasing average crystal size. Nanocrystals are members of a group of nanocrystals. As a result of discrete nucleation and controlled growth,
The resulting population of nanocrystals has a narrow monodisperse diameter distribution. The monodisperse diameter distribution can also be called size. The process of controlled growth and annealing of nanocrystals in a coordinating solvent following nucleation can also result in uniform surface derivatization and regular core structure. To maintain stable growth as the size distribution sharpens,
The temperature can be raised. By adding more M donor or X donor, the growth period can be shortened.

The M donor can be an inorganic compound, an organometallic compound, or an elemental metal. M is
Cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, or thallium. An X donor is a compound that can react with an M donor to produce a substance having the general formula MX. Typically, the X donor is a chalcogenide donor or pnictide donor, such as a phosphine chalcogenide, bis (silyl) chalcogenide, dioxygen, ammonium salt, or tris (silyl) pnictide. Suitable X donors are dioxygen, bis (trimethylsilyl) selenide ((TMS) ₂ Se), trialkylphosphine selenides (eg (tri-n-octylphosphine) selenide (TOPSe) or (tri-n-butylphosphine))
Selenide (TBPSe, etc.), trialkylphosphine telluride (eg (tri-n-octylphosphine) telluride (TOPTe) or hexapropylphosphorustriamide telluride (HPPTTe), etc.), bis (trimethylsilyl) telluride ((TMS) ₂ Te), bis (trimethylsilyl) sulfide ((TMS) ₂ S)), trialkylphosphine sulfide (eg (tri-n-octylphosphine) sulfide (TOPS) etc.), ammonium salt (eg ammonium halide (eg NH ₄ Cl )), Tris (trimethylsilyl) phosphide ((TM
S) ₃ P), tris (trimethylsilyl) arsenide ((TMS) ₃ As), or tris (trimethylsilyl) antimonide ((TMS) ₃ Sb). In certain embodiments, the M donor and the X donor can be components within the same molecule.

Coordinating solvents can help control the growth of nanocrystals. A coordination solvent is a compound having a donor lone electron pair, for example, having a lone electron pair that can be used to coordinate to the surface of the growing nanocrystal. Solvent coordination can stabilize the growing nanocrystals. Typical coordinating solvents include alkyl phosphines, alkyl phosphine oxides, alkyl phosphonic acids, or alkyl phosphinic acids, but other coordinating solvents such as pyridine, furan, and amines are also suitable for the formation of nanocrystals. There may be.
Examples of suitable coordinating solvents are pyridine, tri-n-octylphosphine (TOP), tri-n-octylphosphine oxide (TOPO), and tris-hydroxylpropylphosphine (tHPP). Industrial TOPO can be used.

The size distribution during the growth phase of the reaction can be evaluated by monitoring the absorption line width of the particles. Modification of the reaction temperature in response to changes in the absorption spectrum of the particles makes it possible to maintain a sharp particle size distribution during growth. In order to grow larger crystals, reactants can be added to the nucleation solution during crystal growth. By stopping the growth at a specific nanocrystal average diameter and selecting an appropriate composition of the semiconductor material, the emission spectrum of the nanocrystals extends over a wavelength range of 300 nm to 5 microns, or for CdSe and CdTe, 400 nm to 800 nm. Can be continuously adjusted over time. Nanocrystals have a diameter of less than 150 mm. The group of nanocrystals is 15cm ~
It has an average diameter in the range of 125 mm.

The nanocrystal may be a member of a population of nanocrystals having a narrow size distribution. Nanocrystals can be spherical, rod-shaped, disc-shaped, or other shapes. The nanocrystal can include a core of semiconductor material. The nanocrystal can include a core having the formula MX, where M is cadmium, zinc, magnesium, mercury, aluminum, gallium, indium, thallium, or mixtures thereof, where X is oxygen, sulfur, Selenium, tellurium, nitrogen, phosphorus, arsenic, antimony, or mixtures thereof.

The core can have an overcoating on the surface of the core. The overcoating may be a semiconductor material having a composition different from the composition of the core. The overcoat of semiconductor material on the surface of the nanocrystal is a group II-VI compound, II-V
Group III, Group III-VI compounds, Group III-V compounds, Group IV-VI compounds,
I-III-VI compounds, II-IV-VI compounds, or II-IV-V compounds such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdT
e, MgO, MgS, MgSe, MgTe, HgO, HgS, HgSe, HgTe, Al
N, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, In
P, InAs, InSb, TlN, TlP, TlAs, TlSb, TlSb, PbS, P
bSe, PbTe, or mixtures thereof may be included. For example, ZnS, ZnSe
Alternatively, a CdS overcoating can be grown on CdSe or CdTe nanocrystals. The overcoating process is described, for example, in US Pat. No. 6,322,901. By adjusting the temperature of the reaction mixture during overcoating and monitoring the absorption spectrum of the core, an overcoat material with high emission quantum efficiency and narrow size distribution can be obtained. The overcoating can be 1 to 10 monolayers thick.

The particle size distribution can be further purified by a size selective precipitation method using a poor solvent for nanocrystals such as methanol / butanol as described in US Pat. No. 6,322,901. For example, nanocrystals can be dispersed in 10% butanol in hexane. Methanol can be added dropwise to this stirred solution until the opalescence persists. Separation of the supernatant and aggregates by centrifugation produces a precipitate enriched in the largest crystals in the sample. This procedure can be repeated until no further sharpening of the absorption spectrum is observed. The size selective precipitation method can be carried out with various solvent / non-solvent pairs including pyridine / hexane and chloroform / methanol.
The size-selected nanocrystal population can have a deviation of 15% rms or less from the average diameter, preferably a deviation of 10% rms or less, more preferably a deviation of 5% rms or less.

The outer surface of the nanocrystal can include compounds derived from the coordinating solvent used during the growth process. Surfaces can be modified by repeated exposure to excess competing coordination groups. For example, dispersion of covered nanocrystals can be treated with coordinating organic compounds such as pyridine, easily dispersed in pyridine, methanol, and aromatics, but no longer dispersed in aliphatic solvents. Produces crystals that do not. Such a surface exchange process can be performed using any compound that can coordinate or bind to the external surface of the nanocrystal, including, for example, phosphines, thiols, amines, and phosphates. The nanocrystals can be exposed to short chain polymers that have an affinity for the surface and end with a component that has an affinity for the suspension or dispersion medium. Such affinity improves the stability of the suspension and prevents nanocrystal aggregation. Nanocrystal coordination compounds are described, for example, in US Pat. No. 6,251,303, which is incorporated by reference in its entirety.

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、４、又は５であり；Ｘは、Ｏ、Ｓ、Ｓ＝Ｏ、ＳＯ_２、Ｓｅ、Ｓｅ＝Ｏ、Ｎ、Ｎ＝Ｏ、Ｐ
、Ｐ＝Ｏ、Ａｓ、又はＡｓ＝Ｏであり；Ｙ及びＬはそれぞれ、独立して、アリール、ヘテ
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とも一つの二重結合及び一つの三重結合を任意に含む直鎖状の、又は分岐したＣ_２−１２
炭化水素鎖である。炭化水素鎖は、一種以上のＣ_１−４アルキル、Ｃ_２−４アルケニル、
Ｃ_２−４アルキニル、Ｃ_１−４アルコキシ、ヒドロキシ、ハロ、アミノ、ニトロ、シアノ
、Ｃ_３−５シクロアルキル、３〜５員環ヘテロシクロアルキル、アリール、ヘテロアリー
ル、Ｃ_１−４アルキルカルボニルオキシ、Ｃ_１−４アルキルオキシカルボニル、Ｃ_１−４
アルキルカルボニル、又はホルミルによって任意に置換することができる。また、炭化水
素鎖は、−Ｏ−、−Ｓ−、−Ｎ（Ｒ^ａ）−、−Ｎ（Ｒ^ａ）−Ｃ（Ｏ）−Ｏ−、−Ｏ−Ｃ（
Ｏ）−Ｎ（Ｒ^ａ）−、−Ｎ（Ｒ^ａ）−Ｃ（Ｏ）−Ｎ（Ｒ^ｂ）−、−Ｏ−Ｃ（Ｏ）−Ｏ−、
−Ｐ（Ｒ^ａ）−、又は−Ｐ（Ｏ）（Ｒ^ａ）−によって任意に中断することができる。Ｒ^ａ
及びＲ^ｂはそれぞれ、独立して、水素、アルキル、アルケニル、アルキニル、アルコキシ
、ヒドロキシルアルキル、ヒドロキシル、又はハロアルキルである。 More specifically, the ligand can have the following formula:

Where k is 2, 3, or 5 and n is 1, 2, 3 such that kn is not less than 0.
X is O, S, S = O, SO ₂ , Se, Se = O, N, N = O, P
, P = O, As, or As = O; Y and L are each independently aryl, heteroaryl, or at least one double bond, at least one triple bond, or at least one double bond And a linear or branched C _2-12 optionally containing one triple bond
It is a hydrocarbon chain. The hydrocarbon chain is one or more C _1-4 alkyl, C _2-4 alkenyl,
C _2-4 alkynyl, C _1-4 alkoxy, hydroxy, halo, amino, nitro, cyano, C _3-5 cycloalkyl, 3-5 membered heterocycloalkyl, aryl, heteroaryl, C _1-4 alkylcarbonyloxy C _1-4 alkyloxycarbonyl, C _1-4
It can be optionally substituted by alkylcarbonyl or formyl. In addition, the hydrocarbon chain includes —O—, —S—, —N (R ^a ) —, —N (R ^a ) —C (O) —O—, —O—C (
O) —N (R ^a ) —, —N (R ^a ) —C (O) —N (R ^b ) —, —O—C (O) —O—,
It can be interrupted arbitrarily by -P (R ^<a> )-or -P (O) (R ^<a> )-. R ^a
And R ^b are each independently hydrogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxylalkyl, hydroxyl, or haloalkyl.

The aryl group is a substituted or unsubstituted cyclic aromatic group. Examples are phenyl, benzyl, naphthyl, tolyl, anthracyl, nitrophenyl or halophenyl. A heteroaryl group is an aryl group having one or more heteroatoms in the ring, such as furyl, pyridyl, pyrrolyl, phenanthryl.

Appropriate ligands can be purchased commercially, or can be purchased from ordinary synthetic organic materials such as those described in J. March “Advanced Organic Chemistry”, which is incorporated by reference in its entirety. Can be prepared by techniques.

A transmission electron microscope (TEM) can provide information on the size, shape, and distribution of the nanocrystal population. Powder X-ray diffraction (XRD) patterns can provide the most complete information regarding the type and quality of the crystal structure of the nanocrystal. In addition, since the particle diameter is inversely proportional to the peak width via the X-ray coherence length, the size can be evaluated. For example, the diameter of the nanocrystal can be measured directly by transmission electron microscopy or can be estimated from X-ray diffraction data using, for example, Scherrer's equation. Moreover, it can also evaluate from a UV / Vis absorption spectrum.

Individual devices can be formed at multiple locations on a single substrate to form a photovoltaic array. For some applications, the substrate can include a backplane.
The backplane includes active or passive electronic circuitry for controlling or switching power to or from individual array elements. Including a backplane may be useful in applications such as displays, sensors, or imaging devices. In particular, backplanes are active matrix, passive matrix, fixed format, direct drive (
directly drive) or as a hybrid. See, for example, US patent application Ser. No. 11 / 253,612 filed Oct. 21, 2005, which is incorporated by reference in its entirety.

The device can be made in a controlled (oxygen-free and moisture-free) environment that prevents a reduction in device efficiency during the manufacturing process. Other multilayer structures can also be used to improve device performance (see, for example, US patent application Ser. Nos. 10 / 400,907 and 10 / 400,908 filed Mar. 28, 2003). Each of these patent documents is incorporated by reference). Electron blocking layer (EBL), hole blocking layer (
HBL) or blocking layers such as hole and electron blocking layers (eBL) can be introduced into the structure. The blocking layer may contain 3- (4-biphenylyl) -4-phenyl-5-tertiary-butylphenyl-1,2,4-triazole (
TAZ), 3,4,5-triphenyl-1,2,4-triazole, 3,5-bis (4-
Tert-butylphenyl) -4-phenyl-1,2,4-triazole, batocuproine (BCP), 4,4 ′, 4 ″ -tris {N- (3-methylphenyl) -N-phenylamino} triphenyl Amine (m-MTDATA), polyethylene dioxythiophene (PEDOT
), 1,3-bis (5- (4-diphenylamino) phenyl-1,3,4-oxadiazol-2-yl) benzene, 2- (4-biphenylyl) -5- (4-tertiary- Butylphenyl) -1,3,4-oxadiazole, 1,3-bis [5- (4- (1,1-dimethylethyl) phenyl) -1,3,4-oxadiazol-2-yl] Benzene, 1,
4-Bis (5- (4-diphenylamino) phenyl-1,3,4-oxadiazole-2
-Yl) benzene or 1,3,5-tris [5- (4- (1,1-dimethylethyl) phenyl) -1,3,4-oxadiazol-2-yl] benzene.

The performance of photovoltaic devices can be improved by increasing their efficiency. For example, Bulovic et al., Semiconductors and Semimetals 64, 255 (2000), Adachi
Et al., Appl. Phys. Lett. 78, 1622 (2001), Yamasaki et al., Appl. Phys. Lett.
76, 1243 (2000), Dirr et al., Jpn. J. Appl. Phys. 37, 1457 (1998), and D'Andra.
See de et al., MRS Fall Meeting, BB6.2 (2001). The entirety of each document is incorporated by reference. Nanocrystals can be included in efficient hybrid organic / inorganic light emitting devices.

In order to produce a display, individual devices can be formed at multiple locations on a single substrate. The display can include devices that emit at various wavelengths.
By displaying an array of light emitting semiconductor nanocrystals of different colors on a substrate, a display comprising pixels of different colors can be manufactured.

In order to manufacture a device, for example, a p-type semiconductor such as NiO is used as indium tin oxide
It can be deposited on a transparent electrode such as ITO. The transparent electrode can be disposed on a transparent substrate. Next, microcontact printing or Langmuir jet (
LB) Semiconductor nanocrystals are deposited using a single layer deposition technique that is broadly compatible, such as a technique. Subsequently, an n-type semiconductor (eg ZnO or TiO ₂ ) is applied on top of this layer, for example by sputtering. To complete the device, a metal electrode can be thermally deposited thereon. More complex device structures are possible. For example, a slightly doped layer can be included in proximity to the nanocrystal layer.

The device grows two transport layers individually and polydimethylsiloxane (PDM).
Assembled by physically applying electrical contact using an elastomer such as S). This avoids the need for direct deposition of material on the nanocrystal layer.

The device can be thermally processed after all of the transport layer has been applied. The heat treatment can further enhance charge separation from the nanocrystal and eliminate organic capping groups on the nanocrystal. The instability of the capping group can cause device instability.

The inorganic transport layer used, especially the metal oxide material, is O ₂ and H ₂ O are absorbing layers of the device (
It can act as a barrier layer that prevents entry into the semiconductor nanocrystal layer. The protective nature of the inorganic layer can provide design choices for packaging. For example, the inorganic layer is
Devices can be fabricated without the need for additional components that can be a barrier to water and / or oxygen and prevent such contaminants from reaching the release material. BARIX (Vitex)
Can be made using alternating metal oxide and polymer layers. In such a barrier, the metal oxide becomes a barrier to O ₂ and H ₂ O, and the polymer layer randomizes the occurrence of pinhole defects in the metal oxide layer. Therefore, in using a metal oxide as the transport layer, the device itself functions as a protective layer for the semiconductor nanocrystal.

3A-3E show possible device structures. These are the standard pn diode diagram (FIG. 3A), pin diode diagram (FIG. 3B), transparent device (FIG. 3C), inverted device (FIG. 3D), and flexibility A flexible device (FIG. 3E). For flexible devices, for each single layer metal oxide layer, a slippage layer (slippa
ge layers), ie, a three-layer structure of the metal oxide / metal / metal oxide type. This has been shown to increase the flexibility of metal oxide thin films that increase conductivity while maintaining transparency. This is because the metal layer, usually the silver layer, is very thin (each about 12 nm) and therefore does not absorb much light.

A 60 nm thick indium tin oxide (ITO) electrode was placed on the glass using rf-sputtering in an inert argon environment. Using slow growth rates and low pressures, films with surface roughness of less than 5 nm were achieved, and heating the substrate allowed precise control over the resistivity of ITO. 20 nm nickel oxide (NiO) was rf-sputtered onto the ITO electrode under argon and oxygen to produce a P-type layer. Here, the number of excess hole donor sites is determined by the ratio of O ₂ . Thereafter, colloidally synthesized cadmium zinc selenide (ZnCdSe) nanocrystals tuned to have a red emission were spin coated onto NiO. Slow rotation speeds were used to achieve several monolayers in the nanocrystal range across the device area. Thereafter, insulating zinc oxide (ZnO) and conductive tin oxide (SnO ₂ ) were co-sputtered in an argon environment to obtain a 40 nm film having a carrier concentration similar to that of NiO. Next, a silver top electrode was deposited; however, the device could also be prepared by sputtering an ITO or equivalent conductivity zinc indium oxide top electrode.

FIG. 4 shows the external quantum efficiency spectrum and IV characteristics of the device. The wavelength-dependent external quantum efficiency curve showed a small peak at 625 nm. This indicates that the nanocrystal is involved in the absorption of incident light. The current-voltage plot shows the current response of the device under shading and under illumination. The high dark current (black and blue curves) can be attributed to the fact that the metal oxide layer is thin. An open circuit voltage of 0.2 was guaranteed.
Other embodiments are within the scope of the appended claims.

Claims (32)

A photovoltaic device,
In contact with the first electrode arranged to receive the charge from the first charge transport layer, a first charge transport layer containing a first inorganic material,
In contact with the second electrode arranged to receive the charge from the second charge-transporting layer is disposed between the second charge-transporting layer, and said first charge transport layer and said second charge transport layer A plurality of semiconductor nanocrystals, wherein the nanocrystals are dispersed in the first or second charge transport layer or disposed as a single layer between the first and second electrodes, The photovoltaic device, wherein the photovoltaic device is a substantially monodispersed population of semiconductor nanocrystals, and the outer surface of the nanocrystals comprises a compound having a coordination group.   The photovoltaic device according to claim 1, wherein the first inorganic substance is an inorganic semiconductor.   The photovoltaic device of claim 2, wherein the inorganic semiconductor comprises a metal chalcogenide.   The photovoltaic device of claim 3, wherein the metal chalcogenide is a mixed metal chalcogenide.   The photovoltaic device of claim 3, wherein the metal chalcogenide comprises zinc oxide, titanium oxide, niobium oxide, zinc sulfide, indium tin oxide, or a mixture thereof.   The photovoltaic device of claim 1, wherein the second charge transport layer comprises a second inorganic material.   The photovoltaic device according to claim 6, wherein the second inorganic material is amorphous or polycrystalline.   The photovoltaic device according to claim 7, wherein the second inorganic substance is an inorganic semiconductor.   The photovoltaic device of claim 8, wherein the inorganic semiconductor comprises a metal chalcogenide.   The photovoltaic device of claim 9, wherein the metal chalcogenide is a mixed metal chalcogenide.   The photovoltaic device of claim 9, wherein the metal chalcogenide comprises zinc oxide, titanium oxide, niobium oxide, zinc sulfide, indium tin oxide, or a mixture thereof.   The photovoltaic device of claim 1, wherein the first charge transport layer is a hole transport layer.   The photovoltaic device of claim 1, wherein the first charge transport layer is an electron transport layer.   The photovoltaic device of claim 1, wherein the plurality of semiconductor nanocrystals form a single layer.   The photovoltaic device of claim 1, wherein the device is transparent.   The device of claim 1, wherein the second electrode is in direct contact with the plurality of semiconductor nanocrystals. A device manufacturing method comprising:
Depositing a first charge transport layer comprising a first inorganic material on the electrode;
Depositing a plurality of semiconductor nanocrystal monolayers on the electrode, wherein the plurality of semiconductor nanocrystals is a substantially monodispersed population of semiconductor nanocrystals and the plurality of semiconductor nanocrystals is Depositing a second charge transport layer comprising a second inorganic material over the electrode, wherein the plurality of semiconductor nanocrystals are in contact with the second charge transport layer; In electrical contact with the layer),
The method, wherein the outer surface of the nanocrystal comprises a compound having a coordination group.   The method of claim 17, wherein the device is transparent.   18. The method of claim 17, wherein the second electrode is in direct contact with the plurality of semiconductor nanocrystals. A method of generating a current comprising exposing light of an excitation wavelength to a device comprising:
The device comprises a first charge transport layer containing a first inorganic material in contact with the first electrode arranged to receive the charge from the first charge transport layer;
Disposed between and said first charge transport layer and said second charge transport layer; the second charge-transporting second charge-transporting layer in contact with the second electrode arranged to receive charge from the layer A plurality of semiconductor nanocrystals, wherein the nanocrystals are dispersed within the first or second charge transport layer or disposed as a single layer between the first and second electrodes, the plurality of semiconductor nanocrystals being a semiconductor The method, wherein the method comprises a substantially monodispersed population of nanocrystals, and the outer surface of the nanocrystal comprises a coordination group. 21. The method of claim 20 , wherein the first inorganic material is an inorganic semiconductor. 24. The method of claim 21 , wherein the inorganic semiconductor comprises a metal chalcogenide. 24. The method of claim 22 , wherein the metal chalcogenide is a mixed metal chalcogenide. 23. The method of claim 22 , wherein the metal chalcogenide comprises zinc oxide, titanium oxide, niobium oxide, zinc sulfide, indium tin oxide, or mixtures thereof. 21. The method of claim 20 , wherein the second inorganic material is amorphous or polycrystalline. 26. The method of claim 25 , wherein the second inorganic material is an inorganic semiconductor. 27. The method of claim 26 , wherein the inorganic semiconductor comprises a metal chalcogenide. 28. The method of claim 27 , wherein the metal chalcogenide is a mixed metal chalcogenide. 28. The method of claim 27 , wherein the metal chalcogenide comprises zinc oxide, titanium oxide, niobium oxide, zinc sulfide, indium tin oxide, or mixtures thereof. 21. The method of claim 20 , wherein the device is transparent. 21. The method of claim 20 , wherein the second electrode is in direct contact with the plurality of semiconductor nanocrystals. _2. The photovoltaic according to claim 1, wherein the coordinating group is O, S, S = O, SO2, Se, Se = O, N, N = O, P, P = O, As or As = O. Power device.

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