Patent Description:
A photoelectric conversion device converts light into an electrical signal using photoelectric effects. The photoelectric conversion device includes a photodiode and a phototransistor, and the like, and it may be applied to a sensor or a photodetector.

Sensors are increasingly demanding higher resolution, resulting in smaller pixel sizes. In the case of silicon photodiodes that are currently used, sensitivity reduction may occur because an absorption area decreases as the pixel size decreases. Accordingly, an organic material that is capable of replacing silicon has been researched.

The organic material may have a high extinction coefficient and be configured to selectively absorb light in a particular wavelength region depending on a molecular structure, and thus may simultaneously replace a photodiode and a color filter and resultantly improve sensitivity and contribute to high integration.

However, organic materials may exhibit different characteristics from silicon due to high binding energy and recombination behavior, and it may be difficult to accurately predict the characteristics of organic materials, which may make it difficult to easily control properties required for photoelectric conversion devices. Photoelectric conversion devices have been disclosed already in <CIT>, <CIT> and <CIT>.

Example embodiments provide a photoelectric conversion device capable of reducing remaining charge carriers and improving charge carrier extraction characteristics.

Example embodiments provide a sensor including the photoelectric conversion device.

Example embodiments provide an electronic device including the photoelectric conversion device or the sensor.

According to example embodiments, a photoelectric conversion device includes a first electrode and a second electrode, and a photoelectric conversion layer between the first electrode and the second electrode. The photoelectric conversion layer includes a first material, a second material, and a third material. The first material and the second material form a pn junction. The third material is different from the first material and the second material and the third material is configured to modify a distribution of energy levels of the first material or the second material.

In accordance with the claimed invention, a dipole moment of the third material is greater than or equal to about <NUM> Debye, and the third material is included in an amount of <NUM>% by volume to <NUM>% by volume based on a total volume of the first material and the third material.

In some embodiments, the third material may be configured to modify a distribution of the HOMO energy level of the first material, and the HOMO energy level of the third material may be deeper than the HOMO energy level of the first material or shallower within a range of less than or equal to about <NUM> eV than the HOMO energy level of the first material.

In some embodiments, the HOMO energy level of the third material may be about <NUM> eV to about <NUM> eV, and the HOMO energy level of the first material may be about <NUM> eV to about <NUM> eV.

In some embodiments, the third material provides a modified HOMO energy level of the first material, and the modified HOMO energy level of the first material may be deeper than the HOMO energy level of the first material.

In some embodiments, the modified HOMO energy level of the first material may be between the HOMO energy level of the first material and a HOMO energy level of the second material.

In some embodiments, an absorption spectrum of the photoelectric conversion layer may have a maximum absorption wavelength in a first wavelength region. The first wavelength region may be one of a blue wavelength region, a green wavelength region, a red wavelength region, and an infra-red wavelength region. Each of the first material and the third material may be a light-absorbing material having a maximum absorption wavelength in the first wavelength region.

In some embodiments, the photoelectric conversion layer may include a mixture of the first material, the second material, and the third material.

In some embodiments, a distribution of HOMO energy levels of the photoelectric conversion layer may be different from a distribution of HOMO energy levels of the thin film formed of the first material and the second material.

In some embodiments, the HOMO energy level of the photoelectric conversion layer may be deeper than the HOMO energy level of the thin film formed of the first material and the second material.

In some embodiments, the HOMO energy level of the photoelectric conversion layer may be about <NUM> eV to about <NUM> eV deeper than the HOMO energy level of the thin film formed of the first material and the second material.

In some embodiments, the third material may be an organic material.

In some embodiments, at least one of the first material and the second material may be an organic material.

In some embodiments, the first material may be represented by Chemical Formula A-<NUM>,
<CHM>.

R' to R<NUM> and Ra to Rd independently may be hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a halogen, or a cyano group.

In some embodiments, the second material may include an inorganic material, a thiophene or a thiophene derivative, a fullerene or a fullerene derivative, or a combination thereof.

In some embodiments, the third material may be represented by Chemical Formula <NUM>-<NUM>,
<CHM>.

In some embodiments, the first material and the third material may be a p-type material, and the second material may be an n-type material.

In some embodiments, a HOMO energy level of the third material may be deeper than the HOMO energy level of the first material or the HOMO energy level of the third material may be shallower within a range of less than or equal to about <NUM> eV than a HOMO energy level of the first material.

In some embodiments, the third material may be included in an amount of about <NUM>% by volume to about <NUM>% by volume based on a total volume of the first material and the third material.

In some embodiments, the photoelectric conversion layer may be a ternary system composed of the first material, the second material, and the third material.

In some embodiments, the second material may include an inorganic material, a thiophene or a thiophene derivative, a fullerene or a fullerene derivative, or a combination thereof. The first material may be represented by Chemical Formula A-<NUM>,
<CHM>.

According to example embodiments, a sensor including any one of the above-described photoelectric conversion devices is provided.

According to example embodiments, an electronic device including any one of the above-described photoelectric conversion devices or sensors is provided.

In example embodiments of inventive concepts, remaining charge carriers may be reduced, and charge carrier extraction characteristics may be improved.

Example embodiments will hereinafter be described in detail, and may be easily performed by a person skilled in the related art. However, this disclosure may be embodied in many different forms and is not to be construed as limited to the exemplary embodiments set forth herein.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity.

It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it may be directly on the other element or intervening elements may also be present.

Hereinafter, as used herein, when a definition is not otherwise provided, "substituted" refers to replacement of hydrogen of a compound or a group by a substituent selected from a halogen atom, a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amidino group, a hydrazino group, a hydrazono group, a carbonyl group, a carbamyl group, a thiol group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid group or a salt thereof, a silyl group, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C3 to C20 heteroaryl group, a C3 to C20 heteroarylalkyl group, a C3 to C30 cycloalkyl group, a C3 to C15 cycloalkenyl group, a C6 to C15 cycloalkynyl group, a C3 to C30 heterocycloalkyl group, and a combination thereof.

As used herein, when specific definition is not otherwise provided, "hetero" refers to one including <NUM> to <NUM> heteroatoms selected from N, O, S, Se, Te, Si, and P.

Hereinafter, "combination" refers to a mixture or a stacked structure of two or more.

As used herein, when specific definition is not otherwise provided, an energy level refers to the highest occupied molecular orbital (HOMO) energy level and the lowest unoccupied molecular orbital (LUMO) energy level. As used herein, "the HOMO energy level of the first material" or "the original HOMO energy level of the first material" are used interchangeably, both referring to the HOMO energy level of the first material which is not modified by the third material.

Hereinafter, a work function or an energy level is expressed as an absolute value from a vacuum level. In addition, when the work function or the energy level is referred to be deep, high, or large, it may have a large absolute value based on "<NUM> eV" of the vacuum level while when the work function or the energy level is referred to be shallow, low, or small, it may have a small absolute value based on "<NUM> eV" of the vacuum level.

Hereinafter, when specific definition is not otherwise provided, the work function and the energy level may be values calculated by Turbomole using a B3LYP/def2-SVP basis set.

When the terms "about" or "substantially" are used in this specification in connection with a numerical value, it is intended that the associated numerical value includes a manufacturing or operational tolerance (e.g., ±<NUM>%) around the stated numerical value. Moreover, when the words "generally" and "substantially" are used in connection with geometric shapes, it is intended that precision of the geometric shape is not required but that latitude for the shape is within the scope of the disclosure. Further, regardless of whether numerical values or shapes are modified as "about" or "substantially," it will be understood that these values and shapes should be construed as including a manufacturing or operational tolerance (e.g., ±<NUM>%) around the stated numerical values or shapes.

Hereinafter, a photoelectric conversion device according to an embodiment is described with reference to the drawings.

<FIG> is a cross-sectional view showing an example of a photoelectric conversion device according to example embodiments.

Referring to <FIG>, a photoelectric conversion device <NUM> according to example embodiments includes a first electrode <NUM>, a second electrode <NUM>, and a photoelectric conversion layer <NUM>.

A substrate (not shown) may be disposed at the side of the first electrode <NUM> or the second electrode <NUM>. The substrate may be for example made of an inorganic material such as glass, a silicon wafer, or an organic material such as polycarbonate, polymethylmethacrylate, polyethyleneterephthalate, polyethylenenaphthalate, polyamide, polyethersulfone, or a combination thereof.

The substrate may be omitted. One of the first electrode <NUM> and the second electrode <NUM> is an anode and the other is a cathode. For example, the first electrode <NUM> may be an anode and the second electrode <NUM> may be a cathode. For example, the first electrode <NUM> may be a cathode and the second electrode <NUM> may be an anode.

At least one of the first electrode <NUM> and the second electrode <NUM> may be a transparent electrode. Herein, the transparent electrode may have a high light transmittance of greater than or equal to about <NUM>%. The transparent electrode may include for example at least one of an oxide conductor, a carbon conductor, and a metal thin film. The oxide conductor may include for example at least one of indium tin oxide (ITO), indium zinc oxide (IZO), zinc tin oxide (ZTO), aluminum tin oxide (AlTO), and aluminum zinc oxide (AZO), the carbon conductor may include at least one of graphene and carbon nanostructures, and the metal thin film may be a very thin film including aluminum (Al), magnesium (Mg), silver (Ag), gold (Au), an alloy thereof, or a combination thereof.

One of the first electrode <NUM> and the second electrode <NUM> may be a reflective electrode. Herein, the reflective electrode may have, for example, a light transmittance of less than about <NUM>% or high reflectance of greater than or equal to about <NUM>%. The reflective electrode may include a reflective conductor such as a metal and may include, for example aluminum (Al), silver (Ag), gold (Au), or an alloy thereof.

For example, each of the first electrode <NUM> and the second electrode <NUM> may be a transparent electrode, and one of the first electrode <NUM> and the second electrode <NUM> may be a light-receiving electrode.

For example, the first electrode <NUM> may be a transparent electrode, the second electrode <NUM> may be a reflective electrode, and the first electrode <NUM> may be a light-receiving electrode.

For example, the first electrode <NUM> may be a reflective electrode, the second electrode <NUM> may be a transparent electrode, and the second electrode <NUM> may be a light-receiving electrode.

The photoelectric conversion layer <NUM> may be disposed between the first electrode <NUM> and the second electrode <NUM>. The second electrode <NUM> may be on the first electrode <NUM>.

The photoelectric conversion layer <NUM> may be configured to absorb light in at least one part in a wavelength region and may be configured to convert the absorbed light into an electrical signal. The absorbed light may be configured to convert, for example, a portion of light in a blue wavelength region (hereinafter, referred to as "blue light"), light in a green wavelength region (hereinafter, referred to as "green light"), light in a red wavelength region (hereinafter, referred to as "red light"), and/or light in an infra-red wavelength region (hereinafter, referred to as "infra-red light") into an electrical signal.

For example, the photoelectric conversion layer <NUM> may be configured to selectively absorb at least one of the blue light, the green light, the red light, and the infra-red light and to convert the absorbed light an electrical signal. Herein, the selective absorption of at least one of the blue light, the green light, the red light, and the infra-red light may mean that an absorption spectrum has a maximum absorption wavelength (λmax) in one of the wavelength regions of greater than or equal to about <NUM> and less than about <NUM>, about <NUM> to about <NUM>, greater than about <NUM> and less than or equal to about <NUM>, and greater than about <NUM> and less than or equal to about <NUM>, and an absorption spectrum in the corresponding wavelength region may be remarkably higher than those in the other wavelength regions. Herein "significantly high" may mean that about <NUM>% to about <NUM>%, about <NUM>% to about <NUM>%, about <NUM>% to about <NUM>%, about <NUM>% to about <NUM>%, about <NUM>% to about <NUM>%, or about <NUM>% to about <NUM>% relative to a total area of the absorption spectrum may belong to the corresponding wavelength region.

The photoelectric conversion layer <NUM> may include a first material and a second material forming a pn junction, and the first material and the second material may receive light from the outside to generate excitons. The generated excitons may be separated into holes and electrons. For example, the first material may be a p-type material and the second material may be an n-type material.

For example, each of the first material and the second material may be a light-absorbing material, and for example, at least one of the first material and the second material may be an organic light-absorbing material. For example, at least one of the first material and the second material may be a light-absorbing material having wavelength selectivity which is configured to selectively absorb light in a desired (and/or alternatively predetermined) wavelength region. For example, at least one of the first material and the second material may be an organic light-absorbing material having wavelength selectivity. The absorption spectrum of the first material and the second material may have a maximum absorption wavelength (λmax) in the same or different wavelength regions.

For example, the first material and the second material may be configured to independently selectively absorb one of blue light, green light, red light, and infra-red light. The maximum absorption wavelengths (λmax) of absorption spectra of the first material and the second material may be present in one of the wavelength regions of greater than or equal to about <NUM> and less than about <NUM>, about <NUM> to about <NUM>, greater than about <NUM> and less than or equal to about <NUM>, and greater than about <NUM> and less than or equal to about <NUM>.

For example, the first material and/or the second material may be an organic material.

For example, the first material and/or the second material may be a small molecule compound.

For example, the first material and/or the second material may be a depositable compound.

For example, the first material may be an organic material that has a core structure including an electron donating moiety (EDM), a π-conjugated linking moiety, and an electron accepting moiety (EMA).

The first material may be for example represented by Chemical Formula A, but is not limited thereto.

[Chemical Formula A]     EDM1 - HA1 - EAM1.

For example, the first material represented by Chemical Formula A may be, for example represented by Chemical Formula A-<NUM>, but is not limited thereto.

For example, in Chemical Formula A-<NUM>, Ar1a and Ar2a may independently be one of a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted cinnolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted phthalazinyl group, a substituted or unsubstituted benzotriazinyl group, a substituted or unsubstituted pyridopyrazinyl group, a substituted or unsubstituted pyridopyrimidinyl group, or a substituted or unsubstituted pyridopyridazinyl group.

For example, Ar1a and Ar2a of Chemical Formula A-<NUM> may be linked with each other to form a ring, and for example, Ar1a and Ar2a may be linked with each other by one of a single bond, -O-, -S-, -Se-, -Te-, -N=, -NRe-, -(CRfRg)n2- (where n2 is <NUM> or <NUM>), -SiRhRi-, -GeRjRk-, -(C(Rl)=C(Rm))-, or SnRnRo to form a ring. Herein, Re to R° may independently be hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a halogen, or a cyano group. Also, Rf and Rg, Rh and Ri, Rj and Rk, Rl and Rm, and Rn and R° may independently be present alone or linked with each other to form a ring. For example, Rf and Rg may be linked with each other to form a ring, Rh and Ri may be linked with each other to form a ring, Rj and Rk may be linked with each other to form a ring, Rl and Rm may be linked with each other to form a ring, and/or Rn and R° may be linked with each other to form a ring.

For example, the first material represented by Chemical Formula A-<NUM> may be, for example represented by Chemical Formulae A-<NUM> to A-<NUM>, but is not limited thereto. <CHM>
<CHM>.

In Chemical Formulae A-<NUM> to A-<NUM>,.

For example, Ar<NUM> of Chemical Formula A-<NUM> or A-<NUM> may be benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, pyridine, pyrimidine, or a fused ring of the foregoing two or more.

The second material may include, for example, an organic material, an inorganic material and/or organic/inorganic material, and may be, for example, thiophene or a thiophene derivative, fullerene or a fullerene derivative, but is not limited thereto. The thiophene derivative or the fullerene derivative may be those commonly used in the art and may refer to a thiophene or fullerene compound having a substituent. The substituent may include, for example, a C1 to C30 alkyl group (e.g., a C1 to C20 alkyl group, or a C1 to C10 alkyl group), a C6 to C30 aryl group (e.g., a C6 to C20 aryl group, or a C6 to C12 aryl group), or the like.

The photoelectric conversion layer <NUM> further includes a third material. The third material may be a material different from the first material and the second material, and may be a dopant for modifying physical properties of the first material and/or the second material in the photoelectric conversion layer <NUM>.

The third material may be mixed with the first material and the second material, and thus the third material may be in contact with the first material and/or the second material on an atomic scale to modify morphologies of the first material and/or the second material or molecular conformations of the first material and the second material. Accordingly, diversities of the morphology and the diversity of molecular conformation of the photoelectric conversion layer <NUM> including the first material, the second material, and the third material may be different from the morphology and the diversity of molecular conformation of a thin film made of the first material and the second material (without the third material).

According to a quantum calculation based on such a morphology, the third material having the high dipole moment may be configured to modify the distribution of energy levels of the first material and/or the second material. For example, the third material having the high dipole moment may be configured to modify a distribution of the HOMO energy level or a distribution of the LUMO energy level of the first material or the second material. Accordingly, the distribution of the HOMO energy level or the distribution of the LUMO energy level of the photoelectric conversion layer <NUM> including the first material, the second material, and the third material may be different from the distribution of the HOMO energy level or the distribution of the LUMO energy level of a thin film composed of the first material and the second material (without the third material).

The dipole moment of the third material is greater than or equal to about <NUM> Debye, greater than or equal to about <NUM> Debye, greater than or equal to about <NUM> Debye, greater than or equal to about <NUM> Debye, or greater than or equal to about <NUM> Debye, or within the range of about <NUM> Debye to about <NUM> Debye, about <NUM> Debye to about <NUM> Debye, about <NUM> Debye to about <NUM> Debye, about <NUM> Debye to about <NUM> Debye, or about <NUM> Debye to about <NUM> Debye.

The photoelectric conversion layer <NUM> includes the third material having a high dipole moment as a dopant and thus may be adjusted, so that the first material or the second material may have the distributions of HOMO or LUMO energy levels in a desired region or may not have the distributions of the HOMO or LUMO energy levels in an undesired region.

For example, when the first material is a p-type material and the second material is an n-type material, the third material may be a p-type material that modifies the distribution of HOMO energy levels of the first material. For example, the distribution of the HOMO energy levels of the first material modified by the third material may be shifted toward a deeper HOMO energy level direction compared with the original distribution of the HOMO energy levels of the first material.

In this way, as the distribution of the HOMO energy levels of the first material of the p-type material is shifted, the desired region of the distribution of the HOMO energy levels may be increased, or the undesired region of the distribution of the HOMO energy levels may be reduced or excluded. For example, regions of shallow HOMO energy levels of the p-type material in which relatively lots of trap sites of charge carriers (e.g., holes) are present in the regions of the distribution of the HOMO energy levels thereof may be reduced or excluded. For example, regions of shallower HOMO energy levels than about <NUM> eV in the distribution of the HOMO energy levels of the p-type material may be reduced or excluded.

For example, the distribution of the HOMO energy levels of the first material modified by the third material may be shifted toward a deeper HOMO energy level direction. Herein, the third material may have a deeper or shallower HOMO energy level than HOMO energy level of the first material. For example, the HOMO energy level of the third material may be deeper than HOMO energy level of the first material or the HOMO energy level of the third material may be shallower than HOMO energy level of the first material within a range of less than or equal to about <NUM> eV, for example, the HOMO energy level of the third material may be in a range of about -<NUM> eV to about <NUM> eV (excluding <NUM> eV) compared with HOMO energy level of the first material. For example, the original HOMO energy level of first material may be in a range of about <NUM> eV to about <NUM> eV, and the HOMO energy level of the third material may be in a range of about <NUM> eV to about <NUM> eV. For example, the HOMO energy level of the third material may be deeper than the original HOMO energy level of the first material, for example, the original HOMO energy level of the first material may be in a range of about <NUM> eV to about <NUM> eV, and the HOMO energy level of the third material may be in a range of about <NUM> eV to about <NUM> eV. The HOMO energy levels of the first material modified by the third material may be deeper than the original energy level of the first material. For example, the HOMO energy levels of the first material modified by the third material may be, for example, greater than or equal to about <NUM> eV deeper, for example, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, or about <NUM> eV to about <NUM> eV than the original energy level of the first material.

For example, the HOMO energy level of the second material as an n-type material may be deeper than about <NUM> eV, and the HOMO energy level of the third material may be between the HOMO energy level of the first material and the HOMO energy level of the second material. For example, a difference between the HOMO energy level of the third material and the HOMO energy level of the second material may be smaller than a difference between the HOMO energy level of the first material and the HOMO energy level of the second material. For example, the original HOMO energy level of the first material may be in a range of about <NUM> eV to about <NUM> eV, the HOMO energy level of the second material may be in a range of about <NUM> eV to about <NUM> eV, and the HOMO energy level of the third material may be in a range of about <NUM> eV to about <NUM> eV.

Accordingly, the HOMO energy level of the photoelectric conversion layer <NUM> including the first, second, and third materials may be deeper than that of a thin film formed of the first and second materials (without the third material), for example, greater than or equal to about <NUM> eV deeper, for example, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, about <NUM> eV to about <NUM> eV deeper, or about <NUM> eV to about <NUM> eV deeper than that of a thin film formed of the first and second materials (without the third material).

The third material may be an organic material, an inorganic material and/or organic/inorganic material which have the aforementioned characteristics. The third material may be for example an organic material, for example small molecule compound, for example a depositable organic compound. For example, the photoelectric conversion layer <NUM> may be a co-deposited thin film of the first material, the second material, and the third material.

The third material may be, for example, a light-absorbing material, and may be, for example, a light-absorbing material configured to selectively absorb one of light in a blue wavelength region, a green wavelength region, a red wavelength region, and an infra-red wavelength region.

For example, the absorption spectra of the first material and the third material may have a maximum absorption wavelength (λmax) that in common belongs to one of a blue wavelength region, a green wavelength region, a red wavelength region, and an infra-red wavelength region. For example, the absorption spectra of the first material and the third material may have each maximum absorption wavelength (λmax) in a blue wavelength region of greater than or equal to about <NUM> and less than about <NUM>. For example, the absorption spectra of the first material and the third material may have each maximum absorption wavelength (λmax) in a green wavelength region of about <NUM> to about <NUM>. For example, the absorption spectra of the first material and the third material may have each maximum absorption wavelength (λmax) in a red wavelength region of greater than about <NUM> and less than or equal to about <NUM>. For example, the absorption spectra of the first material and the third material may have each maximum absorption wavelength (λmax) in an infra-red wavelength region of greater than about <NUM> and less than or equal to about <NUM>.

The third material may be, for example, represented by Chemical Formula <NUM>, but is not limited thereto.

[Chemical Formula <NUM>]     EDM3 - HA3 - EAM3.

For example, HA3 may be the same as or different from HA1 described above, EDM3 may be the same as or different from EDM1 described above, and EAM3 may be the same as or different from EAM1 described above. However, at least one of HA3, EDM3, and EAM3 may be different from HA1, EDM1, or EAM1.

For example, the third material represented by Chemical Formula <NUM> may be, for example represented by Chemical Formula <NUM>-<NUM>, but is not limited thereto.

For example, in Chemical Formula <NUM>-<NUM>, Ar1b and Ar2b may independently be a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted quinolinyl group, a substituted or unsubstituted isoquinolinyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted cinnolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted phthalazinyl group, a substituted or unsubstituted benzotriazinyl group, a substituted or unsubstituted pyridopyrazinyl group, a substituted or unsubstituted pyridopyrimidinyl group, and a substituted or unsubstituted pyridopyridazinyl group.

For example, Ar1b and Ar2b of Chemical Formula <NUM>-<NUM> may be linked with each other to form a ring or for example, Ar1b and Ar2b may be linked with each other by one of a single bond, -O-, -S-, -Se-, -Te-, -N=, -NRe-, -(CRfRg)n2- (where n2 is <NUM> or <NUM>), -SiRhRi-, -GeRjRk-, -(C(Rl)=C(Rm))-, or SnRnRo. Herein, Re to R° are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, a halogen, or a cyano group. Also, Rf and Rg, Rh and Ri, Rj and Rk, Rl and Rm, and Rn and R° may independently be present alone or linked with each other to form a ring.

For example, the third material represented by Chemical Formula <NUM>-<NUM> may be for example represented by Chemical Formulae <NUM>-<NUM> to <NUM>-<NUM>, but is not limited thereto. <CHM>
<CHM>
<CHM>.

In Chemical Formulae <NUM>-<NUM> to <NUM>-<NUM>,.

For example, Ar<NUM> of Chemical Formula <NUM>-<NUM>, <NUM>-<NUM>, or <NUM>-<NUM> may be benzene, naphthalene, anthracene, thiophene, selenophene, tellurophene, pyridine, pyrimidine, or a fused ring of the foregoing two or more.

The photoelectric conversion layer <NUM> may be an intrinsic layer in which the aforementioned first, second, and third materials are mixed in the form of a bulk heterojunction.

The first material and the second material may be mixed in a volume ratio of about <NUM>: <NUM> to about <NUM>: <NUM>, for example about <NUM>: <NUM> to about <NUM>: <NUM>, about <NUM>: <NUM> to about <NUM>: <NUM>, about <NUM>: <NUM> to about <NUM>: <NUM>, or about <NUM>: <NUM>.

The third material may be included in an amount that does not affect stability of the molecules of the first material and the second material and other properties required in the photoelectric conversion layer <NUM>, in addition to modifying physical properties of the first material and/or the second material. The third material may be included in an amount that is less than the first material or the second material. The third material is included within the range, about <NUM>% by volume to about <NUM>% by volume, about <NUM>% by volume to about <NUM>% by volume, about <NUM>% by volume to about <NUM>% by volume, about <NUM>% by volume to about <NUM>% by volume, or about <NUM>% by volume to about <NUM>% by volume based on a total volume of the first material and the third material.

For example, the photoelectric conversion layer <NUM> may be a ternary system composed of the first material, the second material, and the third material.

The photoelectric conversion device <NUM> may further include an anti-reflection layer (not shown) on the first electrode <NUM> or under the second electrode <NUM>. The anti-reflection layer may be disposed at a light incidence side and lower reflectance of light of incident light and thereby light absorbance may be further improved. For example, when light is incident to the first electrode <NUM>, the anti-reflection layer may be disposed on the first electrode <NUM>, and when light is incident to the second electrode <NUM>, anti-reflection layer may be disposed under the second electrode <NUM>.

The anti-reflection layer may include, for example a material having a refractive index of about <NUM> to about <NUM>, and may include for example at least one of metal oxide, metal sulfide, and an organic material having a refractive index within the ranges. The anti-reflection layer may include, for example a metal oxide such as aluminum-containing oxide, molybdenum-containing oxide, tungsten-containing oxide, vanadium-containing oxide, rhenium-containing oxide, niobium-containing oxide, tantalum-containing oxide, titanium-containing oxide, nickel-containing oxide, copper-containing oxide, cobalt-containing oxide, manganese-containing oxide, chromium-containing oxide, tellurium-containing oxide, or a combination thereof; metal sulfide such as zinc sulfide; or an organic material such as an amine derivative, but is not limited thereto.

In the photoelectric conversion device <NUM>, when light enters from the first electrode <NUM> or the second electrode <NUM> and the photoelectric conversion layer <NUM> may be configured to absorb light in a desired (and/or alternatively predetermined) wavelength region, excitons may be produced thereinside. The excitons are separated into holes and electrons in the photoelectric conversion layer <NUM>, and the separated holes are transported to an anode that is one of the first electrode <NUM> and the second electrode <NUM> and the separated electrons are transported to the cathode that is the other of the first electrode <NUM> and the second electrode <NUM> so as to flow a current.

Herein, as described above, the photoelectric conversion layer <NUM> further includes the third material capable of modifying properties of the first material and/or the second material, in addition to the first and second materials forming pn junctions, and thus may realize desired properties or exclude undesired properties. Accordingly, the optoelectric characteristics of the photoelectric conversion device <NUM> may be improved. For example, as described above, the distribution of the energy levels of the first material or the second material may be reduced or adjusted, so that regions of energy levels in which relatively lots of trap sites of charge carriers are present in the photoelectric conversion layer <NUM> (e.g., regions of shallow HOMO energy levels) may be reduced or excluded and thus remaining charge carriers may be reduced or prevented from staying or being trapped at the trap sites among charge carriers moving from the photoelectric conversion layer <NUM> to the first electrode <NUM> and/or the second electrode <NUM>. Accordingly, an after-image (an image sticking) due to the remaining charge carriers accumulated in the photoelectric conversion layer <NUM> may be reduced or prevented, resultantly, improving electrical performance of the photoelectric conversion device <NUM>.

<FIG> is a cross-sectional view showing another example of a photoelectric conversion device according to example embodiments.

Referring to <FIG>, a photoelectric conversion device <NUM> according to the embodiment includes a first electrode <NUM>, a second electrode <NUM>, and a photoelectric conversion layer <NUM>, like the aforementioned embodiment. However, the photoelectric conversion device <NUM> according to the present embodiment may further include auxiliary layers <NUM> and <NUM> between the first electrode <NUM> and the photoelectric conversion layer <NUM> and between the second electrode <NUM> and the photoelectric conversion layer <NUM>, unlike the aforementioned embodiment.

The auxiliary layers <NUM> and <NUM> may include a hole injecting layer (HIL) to facilitate the injection of holes, a hole transporting layer (HTL) to facilitate the transport of holes, an electron blocking layer (EBL) to block movement of electrons, electron injecting layer (EIL) to facilitate the injection of electrons, electron transporting layer (ETL) to facilitate the transport of electrons, and/or a hole blocking layer (HBL) to block movement of holes, but are not limited thereto.

The auxiliary layers <NUM> and <NUM> may independently include an organic material, an inorganic material and/or organic/inorganic material.

For example, one of the auxiliary layers <NUM> and <NUM> may include an inorganic auxiliary layer. The inorganic auxiliary layer may include, for example, a lanthanide element, calcium (Ca), potassium (K), aluminum (Al), or an alloy thereof, and the lanthanide element may include, for example, ytterbium (Yb). The inorganic auxiliary layer may have a thickness of less than or equal to about <NUM>.

For example, one of the auxiliary layers <NUM> and <NUM> may include an organic auxiliary layer. The organic auxiliary layer may include, for example, a compound represented by Chemical Formula 2A or 2B, but is not limited thereto. <CHM>
<CHM>
<CHM>.

For example, the organic auxiliary layer may include a compound represented by Chemical Formula 2A-<NUM> or 2B-<NUM>, but is not limited thereto. <CHM>
<CHM>.

In Chemical Formula 2A-<NUM> or 2B-<NUM>,.

For example, the organic auxiliary layer may include a compound represented by Chemical Formula 2A-1a or 2B-1a, but is not limited thereto. <CHM>
<CHM>.

In Chemical Formula 2A-1a and 2B-1a,
R<NUM> to R<NUM> are the same as described in Chemical Formula 2A-<NUM> and 2B-<NUM>, and
Rn and R° are the same as described with respect to Rq and Rr in Chemical Formula 2A and 2B.

For example, one of the auxiliary layers <NUM> and <NUM> may be an inorganic auxiliary layer, and the other of the auxiliary layers <NUM> and <NUM> may be an organic auxiliary layer.

For example, one of the auxiliary layers <NUM> and <NUM> may be omitted.

The aforementioned photoelectric conversion device <NUM> may be applied to, for example, a sensor, and the sensor may be, for example, an image sensor. The image sensor to which the aforementioned photoelectric conversion device <NUM> is applied may be suitable for high speed photographing by reducing an after-image due to remaining charge carriers.

Hereinafter, an example of an image sensor to which the aforementioned device is applied is described with reference to the drawings. An organic CMOS image sensor is described as an example of the image sensor.

<FIG> is a cross-sectional view showing an example of an image sensor according to example embodiments.

Referring to <FIG>, an image sensor <NUM> according to example embodiments includes a semiconductor substrate <NUM>, an insulating layer <NUM>, a photoelectric conversion device <NUM>, and a color filter layer <NUM>.

The semiconductor substrate <NUM> may be a silicon substrate, and is integrated with the transmission transistor (not shown) and the charge storage <NUM>. The transmission transistor and/or the charge storage <NUM> may be integrated in each pixel. The charge storage <NUM> is electrically connected to the photoelectric conversion device <NUM>.

A metal wire (not shown) and a pad (not shown) are formed on the semiconductor substrate <NUM>. In order to decrease signal delay, the metal wire and pad may be made of a metal having low resistivity, for example, aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto.

The insulation layer <NUM> is formed on the metal line and pad. The insulation layer <NUM> may be made of an inorganic insulating material such as a silicon oxide and/or a silicon nitride, or a low dielectric constant (low K) material such as SiC, SiCOH, SiCO, and SiOF. The insulation layer <NUM> has a trench <NUM> exposing the charge storage <NUM>. The trench <NUM> may be filled with fillers.

The aforementioned photoelectric conversion device <NUM> is formed on the insulation layer <NUM>. The photoelectric conversion device <NUM> may have the structure shown in <FIG> or <FIG>, and the detailed description thereof is the same as described above. One of the first electrode <NUM> and the second electrode <NUM> of the photoelectric conversion device <NUM> may be a light-receiving electrode, and the other of the first electrode <NUM> and the second electrode <NUM> of the photoelectric conversion device <NUM> may be connected to the charge storage <NUM>.

The color filter layer <NUM> is formed on the photoelectric conversion device <NUM>. The color filter layer <NUM> includes a blue filter 70a formed in a blue pixel, a red filter 70b formed in a red pixel, and a green filter 70c formed in a green pixel. However, the color filter layer <NUM> may include a cyan filter, a magenta filter, and/or a yellow filter, instead of the above filters, or may further include them in addition to the above filters.

An insulating layer <NUM> is formed between the photoelectric conversion device <NUM> and the color filter layer <NUM>. The insulation layer <NUM> may be omitted.

Focusing lens (not shown) may be further formed on the color filter layer <NUM>. The focusing lens may control a direction of incident light and gather the light in one region. The focusing lens may have a shape of, for example, a cylinder or a hemisphere, but is not limited thereto.

<FIG> is a plan view showing an example of an image sensor according to example embodiments and <FIG> is a cross-sectional view showing an example of the image sensor of <FIG>.

Referring to <FIG> and <FIG>, an image sensor <NUM> according to example embodiments includes a semiconductor substrate <NUM> integrated with photo-sensing devices 150a and 150b, a transmission transistor (not shown), and a charge storage <NUM>, a lower insulation layer <NUM>, a color filter layer <NUM>, an upper insulation layer <NUM>, and the aforementioned photoelectric conversion device <NUM>.

The semiconductor substrate <NUM> may be a silicon substrate, and is integrated with the photo-sensing devices 150a and 150b, the transmission transistor (not shown), and the charge storage <NUM>. The photo-sensing devices 150a and 150b may be photodiodes.

The photo-sensing devices 150a and 150b, the transmission transistor, and/or the charge storage <NUM> may be integrated in each pixel, and as shown in the drawing, the photo-sensing devices 150a and 150b may be respectively included in a blue pixel and a red pixel and the charge storage <NUM> may be included in a green pixel.

The photo-sensing devices 150a and 150b sense light. The information sensed by the photo-sensing devices may be transferred by the transmission transistor. The charge storage <NUM> is electrically connected to the photoelectric conversion device <NUM> that will be described later, and the information of the charge storage <NUM> may be transferred by the transmission transistor.

A metal wire (not shown) and a pad (not shown) are formed on the semiconductor substrate <NUM>. In order to decrease signal delay, the metal wire and pad may be made of a metal having low resistivity, for example, aluminum (Al), copper (Cu), silver (Ag), and alloys thereof, but are not limited thereto. However, it is not limited to the structure, and the metal wire and pad may be disposed under the photo-sensing devices 150a and 150b.

The lower insulation layer <NUM> is formed on the metal wire and the pad. The lower insulation layer <NUM> may be made of an inorganic insulating material such as a silicon oxide and/or a silicon nitride, or a low dielectric constant (low K) material such as SiC, SiCOH, SiCO, and SiOF. The lower insulation layer <NUM> has a trench <NUM> exposing the charge storage <NUM>. The trench <NUM> may be filled with fillers.

A color filter layer <NUM> is formed on the lower insulation layer <NUM>. The color filter layer <NUM> includes a blue filter 70a formed in a blue pixel and a red filter 70b in a red pixel. However, the present disclosure is not limited thereto and may include a cyan filter, a magenta filter and/or a yellow filter instead or additionally. In the present embodiment, a green filter is not included, but a green filter may be further included.

The upper insulation layer <NUM> is formed on the color filter layer <NUM>. The upper insulation layer <NUM> eliminates a step caused by the color filter layer <NUM> and smoothens the surface. The upper insulation layer <NUM> and the lower insulation layer <NUM> may include a contact hole (not shown) exposing a pad, and a trench <NUM> exposing a charge storage <NUM> of a green pixel.

The aforementioned photoelectric conversion device <NUM> is formed on the upper insulating layer <NUM>. The photoelectric conversion device <NUM> may have the structure shown in <FIG> or <FIG>, and the detailed description thereof is the same as described above. One of the first electrode <NUM> and the second electrode <NUM> of the photoelectric conversion device <NUM> may be a light-receiving electrode, and the other of the first electrode <NUM> and the second electrode <NUM> of the photoelectric conversion device <NUM> may be connected to the charge storage <NUM>. An insulating layer <NUM> is formed on the photoelectric conversion device <NUM>. The insulation layer <NUM> may be omitted.

Focusing lens (not shown) may be further formed on the photoelectric conversion device <NUM>. The focusing lens may control a direction of incident light and gather the light in one region. The focusing lens may have a shape of, for example, a cylinder or a hemisphere, but is not limited thereto.

<FIG> is a cross-sectional view showing another example of the image sensor of <FIG>.

Referring to <FIG>, an image sensor <NUM> according to the present embodiment includes a semiconductor substrate <NUM> integrated with photo-sensing devices 150a and 150b, a transmission transistor (not shown), and a charge storage <NUM>, an upper insulation layer <NUM>, and a photoelectric conversion device <NUM>.

However, in the image sensor <NUM> according to the present embodiment, unlike the aforementioned embodiment, the photo-sensing devices 150a and 150b are stacked in the vertical direction, and the lower insulation layer <NUM> and the color filter layer <NUM> are omitted. The photo-sensing devices 150a and 150b are electrically connected to a charge storage (not shown) and may be transferred by a transfer transistor. The photo-sensing devices 150a and 150b may be configured to selectively absorb light in each wavelength region according to the stacking depth.

The photoelectric conversion device <NUM> may have the structure shown in <FIG> or <FIG>, and the detailed description thereof is the same as described above. One of the first electrode <NUM> and the second electrode <NUM> of the photoelectric conversion device <NUM> may be a light-receiving electrode, and the other of the first electrode <NUM> and the second electrode <NUM> of the photoelectric conversion device <NUM> may be connected to the charge storage <NUM>. An insulating layer <NUM> is formed on the photoelectric conversion device <NUM>. The insulation layer <NUM> may be omitted.

<FIG> is a plan view showing another example of an image sensor according to example embodiments, and <FIG> is a cross-sectional view showing an example of the image sensor of <FIG>.

An image sensor <NUM> according to the present embodiment has a structure in which a green photoelectric device configured to selectively absorb light in a green wavelength region, a blue photoelectric device configured to selectively absorb light in a blue wavelength region, and a red photoelectric device configured to selectively absorb light in a red wavelength region are stacked.

The image sensor <NUM> according to the present embodiment includes a semiconductor substrate <NUM>, a lower insulation layer <NUM>, an intermediate insulation layer <NUM>, an upper insulation layer <NUM>, a first photoelectric conversion device 100a, a second photoelectric conversion device 100b, and a third photoelectric conversion device 100c.

The semiconductor substrate <NUM> may be a silicon substrate, and is integrated with the transmission transistor (not shown) and the charge storages 155a, 155b, and 155c.

A metal wire (not shown) and a pad (not shown) are formed on the semiconductor substrate <NUM>, and the lower insulation layer <NUM> is formed on the metal wire and the pad.

The first photoelectric conversion device 100a, the second photoelectric conversion device 100b, and the third photoelectric conversion device 100c are sequentially formed on the lower insulation layer <NUM>.

The first, second, and third photoelectric conversion devices 100a, 100b, and 100c may each independently have the structure shown in <FIG> or <FIG>, and the detailed descriptions thereof are the same as described above. One of the first electrode <NUM> and the second electrode <NUM> of the first, second and third photoelectric conversion devices 100a, 100b, and 100c may be a light-receiving electrode, and the other of the first electrode <NUM> and the second electrode <NUM> of the first, second and third photoelectric conversion devices 100a, 100b, and 100c may be connected to the charge storages 155a, 155b, and 155c.

The first photoelectric conversion device 100a may be configured to selectively absorb light in one of red, blue, and green wavelength regions and may be configured to photoelectrically convert the absorbed light. For example, the first photoelectric conversion device 100a may be a red photoelectric conversion device. The intermediate insulation layer <NUM> is formed on the first photoelectric conversion device 100a.

A second photoelectric conversion device 100b is formed on the intermediate insulation layer <NUM>.

The second photoelectric conversion device 100b may be configured to selectively absorb light in one of red, blue, and green wavelength regions and may be configured to photoelectrically convert the absorbed light. For example, the second photoelectric conversion device 100b may be a blue photoelectric conversion device.

The upper insulation layer <NUM> is formed on the second photoelectric conversion device 100b. The lower insulation layer <NUM>, the intermediate insulation layer <NUM>, and the upper insulation layer <NUM> have a plurality of trenches 85a, 85b, and 85c exposing charge storages 155a, 155b, and 155c.

The third photoelectric conversion device 100c is formed on the upper insulation layer <NUM>. The third photoelectric conversion device 100c may be configured to selectively absorb light in one of red, blue, and green wavelength regions and may photoelectrically convert the absorbed light. For example, the third photoelectric conversion device 100c may be a green photoelectric conversion device.

Focusing lens (not shown) may be further formed on the third photoelectric conversion device 100c. The focusing lens may control a direction of incident light and gather the light in one region. The focusing lens may have a shape of, for example, a cylinder or a hemisphere, but is not limited thereto.

In the drawing, the first photoelectric conversion device 100a, the second photoelectric conversion device 100b, and the third photoelectric conversion device 100c are sequentially stacked, but the present disclosure is not limited thereto, and they may be stacked in various orders.

As described above, the first photoelectric conversion device 100a, the second photoelectric conversion device 100b, and the third photoelectric conversion device 100c are stacked, and thus the size of an image sensor may be reduced to realize a down-sized image sensor.

<FIG> is a plan view showing another example of an image sensor according to example embodiments and <FIG> is a cross-sectional view showing an example of the image sensor of <FIG>.

Referring to <FIG> and <FIG>, an image sensor <NUM> includes a photoelectric conversion device <NUM> disposed on a semiconductor substrate <NUM>, and the photoelectric conversion device <NUM> includes a plurality of photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM>. The plurality of the photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM> may convert light (e.g., blue light, green light, or red light) in different wavelength regions into an electrical signal. Referring to <FIG>, a plurality of the photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM> may be arranged on the semiconductor substrate <NUM> in a horizontal direction such that the photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM> may be partially or entirely overlapped with each other in a direction extending in parallel with the surface 110a of the semiconductor substrate <NUM>. Each photoelectric conversion device <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM> is connected to a charge storage <NUM> integrated in the semiconductor substrate <NUM> through a trench <NUM>.

Each photoelectric conversion device <NUM>-<NUM>, <NUM>-<NUM>, <NUM>-<NUM> may be one of the aforementioned photoelectric conversion devices <NUM> and <NUM>. For example, two or more of photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM> may include different portions of a common, continuous layer that extends continuously between the photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM>. For example, the plurality of photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM> may share a common first electrode <NUM> and/or a common second electrode <NUM>. For example, two or more of the photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM> may have different photoelectric conversion layer <NUM> configured to absorb different wavelength regions of incident light. Other configurations of the image sensor <NUM> may be the same as one or more of the image sensors described with reference to <FIG>.

Referring to <FIG>, an image sensor <NUM> includes a semiconductor substrate <NUM> and photoelectric conversion devices <NUM>-<NUM> and <NUM> which are stacked on the semiconductor substrate <NUM>. The photoelectric conversion device <NUM> includes a plurality of photoelectric conversion devices <NUM>-<NUM> and <NUM>-<NUM> and the plurality of photoelectric conversion devices <NUM>-<NUM> and <NUM>-<NUM> may be arranged to be overlapped with each other in a direction extending in parallel with the surface 110a of the semiconductor substrate <NUM>. The plurality of the photoelectric conversion devices <NUM>-<NUM>, <NUM>-<NUM>, and <NUM>-<NUM> may convert light (e.g., blue light, green light, or red light) in different wavelength regions into an electrical signal.

As an example, the photoelectric conversion device <NUM>-<NUM> may include horizontally-arranged, plurality of photoelectric conversion devices configured to absorb light in different wavelength regions. As an example, the photoelectric conversion device <NUM> may photoelectrically convert light of one wavelength region selected from blue light, green light, and red light. As an example, the photoelectric conversion device <NUM> may be partially or entirely overlapped with the photoelectric conversion device <NUM>-<NUM>. Other configurations of the image sensor <NUM> may be the same as one or more of the image sensors described with reference to <FIG>.

<FIG> is a cross-sectional view showing another example of an image sensor according to example embodiments.

Referring to <FIG>, an image sensor <NUM> includes a semiconductor substrate <NUM> integrated with photo-sensing devices 150a and 150b, a transmission transistor (not shown), and a charge storage <NUM>; an upper insulation layer <NUM> and a color filter layer <NUM> which are disposed on the semiconductor substrate <NUM>; a lower insulation layer <NUM> and a photoelectric conversion device <NUM> which are disposed under the semiconductor substrate <NUM>. The photoelectric conversion device <NUM> may be the aforementioned photoelectric conversion devices <NUM> and <NUM>. As shown in <FIG>, the photoelectric conversion device <NUM> is disposed under the semiconductor substrate <NUM> and thereby the photoelectric conversion device <NUM> and the color filter layer <NUM> are separated with respect to the photo-sensing devices 150a and 150b. Other configurations of the image sensor <NUM> may be the same as one or more of the image sensors described with reference to <FIG>.

The aforementioned photoelectric conversion device and sensor may be applied to various electronic devices, for example a mobile phone, a camera (as depicted in <FIG>), a biometric device, and/or automotive electronic parts, but is not limited thereto.

<FIG> is a schematic diagram showing an electronic device according to example embodiments.

Referring to <FIG>, an electronic device <NUM> may include a processor <NUM>, a memory <NUM>, and an image sensor <NUM> that are electrically coupled together via a bus <NUM>. The image sensor <NUM> may be one according to one of the aforementioned embodiments. The memory <NUM>, which may be a non-transitory computer readable medium, may store a program of instructions. The memory <NUM> may be a nonvolatile memory, such as a flash memory, a phase-change random access memory (PRAM), a magneto-resistive RAM (MRAM), a resistive RAM (ReRAM), or a ferro-electric RAM (FRAM), or a volatile memory, such as a static RAM (SRAM), a dynamic RAM (DRAM), or a synchronous DRAM (SDRAM). The processor <NUM> may execute the stored program of instructions to perform one or more functions. For example, the processor <NUM> may be configured to process electrical signals generated by the image sensor <NUM>. The processor <NUM> may be configured to generate an output (e.g., an image to be displayed on a display interface) based on such as processing.

<FIG> is a block diagram of a digital camera including an image sensor according to an embodiment.

Referring to <FIG>, a digital camera <NUM> includes a lens <NUM>, an image sensor <NUM>, a motor <NUM>, and an engine <NUM>. The image sensor <NUM> may be one according to one of the aforementioned embodiments.

The lens <NUM> concentrates incident light on the image sensor <NUM>. The image sensor <NUM> generates RGB data for received light through the lens <NUM>. In some embodiments, the image sensor <NUM> may interface with the engine <NUM>. The motor <NUM> may adjust the focus of the lens <NUM> or perform shuttering in response to a control signal received from the engine <NUM>. The engine <NUM> may control the image sensor <NUM> and the motor <NUM>. The engine <NUM> may be connected to a host/application <NUM>.

In example embodiments, processor <NUM> of <FIG>, the motor <NUM>, engine <NUM>, and host/application <NUM> may include processing circuitry such as hardware including logic circuits; a hardware/software combination such as a processor executing software; or a combination thereof. For example, the processing circuitry more specifically may include, but is not limited to, a central processing unit (CPU) , an arithmetic logic unit (ALU), a digital signal processor, a microcomputer, a field programmable gate array (FPGA), a System-on-Chip (SoC), a programmable logic unit, a microprocessor, application-specific integrated circuit (ASIC), etc..

However, these examples are non-limiting examples, and inventive concepts are not limited thereto.

A simulation evaluation is performed by assuming Compound B as a first material; fullerene C<NUM> as a second material; and one of Compounds C-<NUM> to C-<NUM> as a third material, molecular-dynamically predicting atomistic morphology based on molecular structures of the first, second, and third materials in each thin film including the first, second, and third materials according to Table <NUM>, and performing a quantum calculation with respect to all the molecules included in the morphology to obtain an energy level distribution. Herein, the first material and the second material are included in a volume ratio of <NUM>:<NUM>, and the third material is included in <NUM> volume% based on a total volume of the first and third materials.

The quantum calculation is performed by considering conformation and a surrounding environment of each molecule of the morphology. Accordingly, the energy level distribution may be evaluated by considering a conformation change of the first material depending on influences of the third material or a surrounding environment change of the molecules.

Properties of the first material, the second material, and the third material are shown in Table <NUM>.

A simulation calculation of HOMO energy level distribution is performed by using a Quantum patch software (Nanomatch GmbH), and a simulation calculation of dipole moments of molecules is performed by using a Jaguar software (Schrodinger, LLC. Materials science suite). However, the Quantum patch software of B3LYP/def2-SVP and the Jaguar software of LACV3P** basis set performs a Density Functional Theory (DFT) calculation.

A remaining charge carrier change depending on changes in the distribution of a HOMO energy level of the first material is evaluated through a simulation.

<FIG> is a graph showing changes in distributions of HOMO energy levels of the first material, and <FIG> and <FIG> are graphs showing changes in remaining charge carriers depending on changes in the distribution of HOMO energy levels of the first material.

Referring to <FIG> and <FIG>, as the HOMO energy level distribution of the first material is shifted toward a deeper direction, remaining charge carrier characteristics may be improved.

Energy level changes of the first material and remaining charge carrier changes depending on the energy level changes are evaluated.

Referring to Table <NUM>, as HOMO energy level of the first material becomes deeper, remaining charge carriers characteristics may be improved, and as the HOMO energy level change of the first material is larger, the remaining charge carrier characteristics may be further improved.

Photoelectric conversion devices are manufactured to experimentally verify the simulation evaluations.

An ITO is sputtered on a glass substrate to form a <NUM>-thick anode. On the anode, Compound A is deposited to form a <NUM>-thick charge blocking layer. On the charge blocking layer, Compound B (the first material) (λmax: <NUM>), fullerene (C<NUM>, the second material), and Compound C-<NUM> (the third material) (λmax: <NUM>) are co-deposited to form a <NUM>-thick photoelectric conversion layer. Herein, the first material and the second material are co-deposited in a volume ratio (a thickness ratio) of <NUM>:<NUM>, and the third material is co-deposited in an amount of <NUM> volume% based on the total volume of the first and third materials. The modified HOMO energy level of the first material in the photoelectric conversion layer is <NUM> eV and LUMO energy level of fullerene is <NUM> eV. On the photoelectric conversion layer, Yb is thermally deposited to form a <NUM>-thick electron buffer layer (work function: <NUM> eV). On the electron buffer layer, ITO is sputtered to form a <NUM>-thick cathode. Subsequently, on the cathode, aluminum oxide (Al<NUM>O<NUM>) is deposited to form a <NUM>-thick anti-reflection layer and then, sealed with a glass plate and thus manufacture a photoelectric conversion device.

A photoelectric conversion device is manufactured according to the same method as Device Example <NUM> except that the photoelectric conversion layer is formed by using Compound C-<NUM> (λmax: <NUM>) instead of Compound C-<NUM> as the third material. The modified HOMO energy level of the first material in the photoelectric conversion layer is <NUM> eV.

A photoelectric conversion device is manufactured according to the same method as Device Example <NUM> except that a photoelectric conversion layer is formed by using Compound C-<NUM> (λmax: <NUM>) instead of Compound C-<NUM> as the third material. The modified HOMO energy level of the first material in the photoelectric conversion layer is <NUM> eV.

A photoelectric conversion device is manufactured according to the same method as Device Example <NUM> except that a photoelectric conversion layer is formed by co-deposing the first and second materials without the third material. The modified HOMO energy level of the first material in the photoelectric conversion layer is <NUM> eV.

A photoelectric conversion device is manufactured according to the same method as Device Example <NUM> except that a photoelectric conversion layer is formed by using Compound C-<NUM> instead of Compound C-<NUM> as the third material. The modified HOMO energy level of the first material in the photoelectric conversion layer is <NUM> eV.

Remaining charge carrier characteristics of the photoelectric conversion devices according to Device Examples and Device Comparative Examples are evaluated.

The remaining charge carrier characteristics are evaluated by measuring an amount of charge carriers not used in a signal treatment but still read in the next frame out of the photoelectrically converted charge carriers in one frame and specifically, by irradiating the devices of Examples and Comparative Examples with photoelectrically convertible light of a green wavelength region for <NUM> milliseconds and then, measuring a current amount by a unit of <NUM>-<NUM> second with a Keithley <NUM> equipment. An amount of the remaining electrons is evaluated at <NUM> lux by a h+/s/µm<NUM> unit.

Referring to Table <NUM>, the devices of Device Examples exhibit improved remaining electron characteristics compared with those of Device Comparative Examples. In addition, Device Examples exhibit substantially equivalent results to the simulation results.

Claim 1:
A photoelectric conversion device (<NUM>), comprising a first electrode (<NUM>) and a second electrode (<NUM>); and a photoelectric conversion layer (<NUM>) between the first electrode and the second electrode,
the photoelectric conversion layer including a first material, a second material, and a third material,
the first material and the second material forming a pn junction, and
the third material being different from the first material and the second material, and
the third material being configured to modify a distribution of energy levels of the first material or the second material,
wherein the third material is included in an amount of <NUM>% by volume to <NUM>% by volume based on a total volume of the first material and the third material, and characterized in that a dipole moment of the third material is greater than or equal to <NUM> Debye.