Patent Application
20240215276
This application claims priority to and the benefit of Korean Patent Application No. 10-2022-0165100, filed on Nov. 30, 2022, in the Korean Intellectual Property Office, the disclosure of which is incorporated by reference herein in its entirety.
One or more embodiments of the present disclosure relate to an organic photodetector and an electronic apparatus including the same.
Photoelectric devices, which convert light and an electrical signal, may include a photodiode and a phototransistor and may be applied to an image sensor, a solar cell, an organic light-emitting device, and/or the like.
In the case of silicon, which is utilized in photodiodes, as the size of pixels decreases, an absorption area may decrease, thus deteriorating sensitivity. Accordingly, organic materials that may replace silicon are being studied.
Because organic materials have a relatively large extinction coefficient and may selectively absorb light in a specific wavelength region according to the molecular structure thereof, organic materials may replace photodiodes and color filters concurrently (e.g., simultaneously), which may facilitate improvements in sensitivity and high integration.
An organic photodetector (OPD) including such an organic material may be applied to, for example, a display apparatus or an image sensor.
Aspects of embodiments may be directed toward an organic photodetector with substantially improved efficiency and an electronic apparatus including the same.
Additional aspects will be set forth in part in the description, which follows and, in part, will be apparent from the description, or may be learned by practice of the presented embodiments of the disclosure.
According to one or more embodiments, an organic photodetector includes
In an embodiment, the activation layer and the optical auxiliary layer may be in contact with each other.
In an embodiment, the activation layer and the second optical auxiliary layer may be in contact with each other.
In an embodiment, the activation layer may include a layer including the p-type semiconductor compound and a layer including the n-type semiconductor compound, and
In an embodiment, the HOMO energy absolute value of the first amine compound may be 5.00 eV or more.
In an embodiment, the HOMO energy absolute value of the second amine compound may be 5.20 eV or more.
In an embodiment, the first optical auxiliary layer and the second optical auxiliary layer may be in contact with each other.
In an embodiment, the first electrode may be an anode, the second electrode may be a cathode, the organic photodetector may further include a hole transport region arranged between the optical auxiliary layer and the first electrode, and the hole transport region may include a hole injection layer, a hole transport layer, an electron blocking layer, or any combination thereof.
In an embodiment, the first electrode may be an anode, the second electrode may be a cathode, the organic photodetector may further include an electron transport region arranged between the activation layer and the second electrode, and the electron transport region may include a buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, or any combination thereof.
In an embodiment, the p-type semiconductor compound may include boron subphthalocyanine chloride (SubPc), copper(II)phthalocyanine (CuPc), tetraphenyldibenzoperiflanthene (DBP), a compound represented by Formula 1, or any combination thereof.
In Formula 1,
In an embodiment, Z111 in Formula 1 may be represented by one of Formulae 111A to 111F.
In Formulae 111A to 111F,
In an embodiment, the n-type semiconductor compound may include C60 fullerene, C70 fullerene, a compound represented by Formula 2, a compound represented by Formula 3, or any combination thereof.
In Formula 2,
In an embodiment, each of the compound represented by Formula 2 and the compound represented by Formula 3 may include one of compounds.
In an embodiment, the first amine compound may be a tertiary amine compound including one or two fluorene moieties, and at least one aryl moiety.
In an embodiment, the second amine compound may be a tertiary amine compound including three fluorene moieties.
In an embodiment, the first amine compound may include one of compounds.
In an embodiment, the second amine compound may include one of compounds.
According to one or more embodiments, there is provided an electronic apparatus including the organic photodetector.
In an embodiment, the electronic apparatus may further include a light-emitting device.
According to one or more embodiments, an electronic apparatus includes a substrate including a photodetection area and an emission area,
The above and other aspects, features, and advantages of certain embodiments of the disclosure will be more apparent from the following description taken in conjunction with the accompanying drawings, in which:
Reference will now be made in more detail to embodiments, examples of which are illustrated in the accompanying drawings, wherein like reference numerals refer to like elements throughout, and duplicative descriptions thereof may not be provided the specification. In this regard, the present embodiments may have different forms and should not be construed as being limited to the descriptions set forth herein. Accordingly, the embodiments are merely described, by referring to the drawings, to explain aspects of the present description. any Further, the use of “may” when describing embodiments of the inventive concept refers to “one or more embodiments of the present disclosure.”
As utilized herein, the term “and/or” includes anynd all combinations of one or more of the associated listed items. Throughout the disclosure, the expression “at least one of a, b or c”, “at least one of a-c”, “at least one of a to c”, “at least one of a, b, and/or c”, etc., indicates only a, only b, only c, both (e.g., simultaneously) a and b, both (e.g., simultaneously) a and c, both (e.g., simultaneously) b and c, all of a, b, and c, or variations thereof.
In the present specification, “including A or B”, “A and/or B”, etc., represents A or B, or A and B.
Spatially relative terms, such as “beneath”, “below”, “lower”, “downward”, “above”, “upper”, “left”, “right”, and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the other elements or features. Thus, the example term “below” can encompass both an orientation of above and below. The device may be otherwise oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
Unless explicitly described to the contrary, the word “comprise”, and variations such as “comprises” or “comprising”, will be understood to imply the inclusion of stated elements but not the exclusion of any other elements.
As used herein, the term “substantially,” “about,” and similar terms are used as terms of approximation and not as terms of degree, and are intended to account for the inherent deviations in measured or calculated values that would be recognized by those of ordinary skill in the art. “About” or “substantially”, as used herein, is inclusive of the stated value and means within an acceptable range of deviation for the particular value as determined by one of ordinary skill in the art, considering the measurement in question and the error associated with measurement of the particular quantity (i.e., the limitations of the measurement system). For example, “about” or “substantially” may mean within one or more standard deviations, or within ±30%, 20%, 10%, 5% of the stated value.
Depending on context, a divalent group may refer or be a polyvalent group (e.g., trivalent, tetravalent, etc., and not just divalent) per, e.g., the structure of a formula in connection with which of the terms are utilized.
The disclosure may include one or more suitable modifications and one or more suitable embodiments, and specific embodiments will be illustrated in the drawings and described in more detail in the detailed description. Effects and features of the disclosure, and methods of achieving the same will be clarified by referring to embodiments described in more detail later with reference to the drawings. The disclosure may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
As utilized herein, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise.
As utilized herein, the terms “comprise”, “include”, “have”, and/or the like, specify the presence of stated features and/or elements, and do not exclude the presence of addition of one or more other features and/or elements.
It will be understood that when a layer, region, or element is referred to as being “on” or “onto” another layer, region, or element, it may be directly or indirectly formed over the other layer, region, or element. For example, for example, intervening layers, regions, or elements may be present.
Like reference numerals in the drawings denote like elements, and thus their description will not be provided.
Sizes of elements in the drawings may be exaggerated for convenience of explanation. In other words, the sizes and thicknesses of elements are arbitrarily illustrated in the drawings for the convenience of explanation, and the disclosure is not limited thereto.
Referring to
The activation layer 140 generates excitons by receiving light from the outside and divides the generated excitons into holes and electrons. The activation layer 140 may include a p-type semiconductor (e.g., p-semiconductor) compound and an n-type semiconductor (e.g., n-semiconductor) compound.
The first optical auxiliary layer 131 faces the first electrode 110. In other words, the first electrode 110 is closer to the first optical auxiliary layer 131 among the first optical auxiliary layer 131 and the second optical auxiliary layer 132 (e.g., the first electrode 110 is closer to the first optical auxiliary layer 131 than to the second optical auxiliary layer 132).
The optical auxiliary layer 130 may compensate for an optical resonance distance according to a wavelength of light introduced to the activation layer 140 to increase light introduction efficiency.
For example, a total thickness of the optical auxiliary layer 130 may be about 100 Å to about 500 Å, and a thickness of the first optical auxiliary layer 131 and a thickness of the second optical auxiliary layer 132 may each independently be 10 Å to 490 Å. When the thickness of the optical auxiliary layer 130 is within the range described above, the thickness may be appropriate or suitable as a resonance thickness.
In
The activation layer 140 may include a p-type semiconductor compound and an n-type semiconductor compound. For example, the activation layer 140 may be a mixed layer including the p-type semiconductor compound and the n-type semiconductor compound, or may include a layer including the p-type semiconductor compound and a layer including the n-type semiconductor compound.
The layer including the p-type semiconductor compound and the layer including the n-type semiconductor compound may form a PN junction. Excitons may be efficiently separated into holes and electrons by photo-induced charge separation occurring at an interface between these layers.
When the activation layer 140 is a mixed layer, excitons may be generated within a diffusion distance from a p-type semiconductor compound-n-type semiconductor compound interface, and thus, the organic photodetector 10 may have improved efficiency. A ratio of the p-type semiconductor compound-n-type semiconductor compound may be, for example, 10:90 to 90:10 (weight ratio).
For example, the activation layer 140 may be a mixed layer consisting of the p-type semiconductor compound and the n-type semiconductor compound. For example, the activation layer 140 may include (e.g., consist of) a layer consisting of the p-type semiconductor compound and a layer consisting of the n-type semiconductor compound.
In an embodiment, the activation layer 140 and the optical auxiliary layer 130 may be in direct contact with each other. For example, the activation layer 140 and the second optical auxiliary layer 132 may be in direct contact with each other.
When the activation layer 140 includes a layer including the p-type or kind semiconductor compound and a layer including the n-type semiconductor compound, the layer including the p-type semiconductor compound may be in direct contact with the second optical auxiliary layer 132.
A total thickness of the activation layer 140 may be about 200 Å to about 2,000 Å, for example, about 400 Å to about 600 Å. When the activation layer 140 includes a layer including the p-type semiconductor compound and a layer including the n-type semiconductor compound, a thickness of the layer including the p-type semiconductor compound and a thickness of the layer including the n-type semiconductor compound may each independently be about 50 Å to about 1,000 Å, for example, about 100 Å to about 400 Å.
When the thickness of the activation layer 140 is within the range described above, absorption of incident light may be efficient, and for example, absorption of green light may be efficient. A wavelength of the green light may be, for example, about 490 nm to about 560 nm.
For example, the first optical auxiliary layer 131 may include (e.g., consist of) a first amine compound, and the second optical auxiliary layer 132 may include (e.g., consist of) a second amine compound.
In the organic photodetector 10 according to an embodiment, when a HOMO energy absolute value of the first amine compound of the first optical auxiliary layer 131 is smaller than a HOMO energy absolute value of the second amine compound of the second optical auxiliary layer 132, and the first optical auxiliary layer 131 faces the first electrode 110, energy barrier may be reduced, and efficiency may increase.
In an embodiment, the HOMO energy absolute value of the first amine compound may be 5.00 eV or more.
In an embodiment, the HOMO energy absolute value of the second amine compound may be 5.20 eV or more.
In an embodiment, the first optical auxiliary layer 131 and the second optical auxiliary layer 132 may be in direct contact with each other.
One of the first electrode 110 and the second electrode 170 may be an anode, and the other one may be a cathode. For example, the first electrode 110 may be an anode, and the second electrode 170 may be a cathode.
A hole transport region of the organic photodetector 10 may include a structure in which a hole injection layer, the hole transport layer 120, an electron blocking layer, or any combination thereof is disposed above the first electrode 110. For example, the hole injection layer may be arranged between the first electrode 110 and the hole transport layer 120.
For example, the hole transport layer 120 may include a layer including a p-dopant. The layer including the p-dopant may be in direct contact with the first electrode 110.
For example, a HOMO energy absolute value of the electron transport layer 160 may be smaller than a HOMO energy absolute value of the first amine compound.
The p-dopant will be described.
An electron transport region of the organic photodetector 10 may include a structure in which the buffer layer 150, a hole blocking layer, the electron transport layer 160, an electron injection layer, or any combination thereof is arranged above the activation layer 140. For example, the electron injection layer may be arranged between the second electrode 170 and the electron transport layer 160.
In an embodiment, the p-type semiconductor compound may include boron subphthalocyanine chloride (SubPc), copper(II)phthalocyanine (CuPc), tetraphenyldibenzoperiflanthene (DBP), a compound represented by Formula 1, or any combination thereof:
In an embodiment, Z111 in Formula 1 may be represented by one of Formulae 111A to 111F:
In an embodiment, the compound represented by Formula 1 may include one of compounds of Group 1 to Group 3:
For example, a HOMO energy absolute value of the p-type semiconductor compound may be greater than a HOMO energy absolute value of the second amine compound.
In an embodiment, the n-type semiconductor compound may include C60 fullerene, C70 fullerene, a compound represented by Formula 2, a compound represented by Formula 3, or any combination thereof:
In an embodiment, each of the compound represented by Formula 2 and the compound represented by Formula 3 may include one of compounds:
In the organic photodetector 10 according to an embodiment, as long as the HOMO energy absolute values of the first and second amine compounds are satisfied as described above, structures thereof may be irrelevant.
In an embodiment, the first amine compound may be a tertiary amine compound including: one or two fluorene moieties; and at least one aryl moiety.
In an embodiment, the second amine compound may be a tertiary amine compound including three fluorene moieties.
For example, the first amine compound may have a structure of Formula 4, and may include at least one aryl moiety and one or two fluorene moieties.
In Formula 4, Ar11 to Ar13 may each independently be a C3-C60 carbocyclic group or a C1-C60 heterocyclic group,
R10a may be the same as described in connection with Formula 1.
For example, the second amine compound may be a tertiary amine compound having a structure of Formula 4 and including three fluorene moieties.
A fluorene moiety may include a spiro-compound.
In an embodiment, the first amine compound may include one of compounds:
In an embodiment, the second amine compound may include one of compounds:
In an embodiment, the p-dopant may include a quinone derivative, a cyano group-containing compound, a compound including an element EL1 and an element EL2, or any combination thereof.
Examples of the quinone derivative may include TCNQ, F4-TCNQ, and/or the like.
Examples of the cyano group-containing compound may include HAT-CN, a compound represented by Formula 221, and/or the like.
In Formula 221,
In the compound containing an element EL1 and an element EL2, the element EL1 may be metal, metalloid, or a combination thereof, and the element EL2 may be non-metal, metalloid, or a combination thereof.
Examples of the metal may include an alkali metal (for example, lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), etc.); an alkaline earth metal (for example, beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), etc.); a transition metal (for example, titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), technetium (Tc), rhenium (Re), iron (Fe), ruthenium (Ru), osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), etc.); a post-transition metal (for example, zinc (Zn), indium (In), tin (Sn), etc.); and a lanthanide metal (for example, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc.).
Examples of the metalloid may include silicon (Si), antimony (Sb), and tellurium (Te).
Examples of the non-metal may include oxygen (O) and a halogen (for example, F, Cl, Br, I, etc.).
In an embodiment, examples of the compound containing the element EL1 and the element EL2 may include a metal oxide, a metal halide (for example, a metal fluoride, a metal chloride, a metal bromide, or a metal iodide), a metalloid halide (for example, a metalloid fluoride, a metalloid chloride, a metalloid bromide, or a metalloid iodide), a metal telluride, or any combination thereof.
Examples of the metal oxide may include a tungsten oxide (for example, WO, W2O3, WO2, WO3, W2O5, etc.), a vanadium oxide (for example, VO, V2O3, VO2, V2O5, etc.), a molybdenum oxide (MoO, Mo2O3, MoO2, MoO3, Mo2O5, etc.), and a rhenium oxide (for example, ReO3, etc.).
Examples of the metal halide may include an alkali metal halide, an alkaline earth metal halide, a transition metal halide, a post-transition metal halide, and a lanthanide metal halide.
Examples of the alkali metal halide may include LiF, NaF, KF, RbF, CsF, LiCl, NaCl, KCl, RbCl, CsCl, LiBr, NaBr, KBr, RbBr, CsBr, LiI, NaI, KI, RbI, and CsI.
Examples of the alkaline earth metal halide may include BeF2, MgF2, CaF2, SrF2, BaF2, BeCl2, MgCl2, CaCl2, SrCl2, BaCl2, BeBr2, MgBr2, CaBr2, SrBr2, BaBr2, BeI2, MgI2, CaI2, SrI2, and BaI2.
Examples of the transition metal halide may include a titanium halide (for example, TiF4, TiCl4, TiBr4, TiI4, etc.), a zirconium halide (for example, ZrF4, ZrCl4, ZrBr4, ZrI4, etc.), a hafnium halide (for example, HfF4, HfCl4, HfBr4, HfI4, etc.), a vanadium halide (for example, VF3, VCl3, VBr3, VI3, etc.), a niobium halide (for example, NbF3, NbCl3, NbBr3, NbI3, etc.), a tantalum halide (for example, TaF3, TaCl3, TaBr3, TaI3, etc.), a chromium halide (for example, CrF3, CrCl3, CrBr3, CrI3, etc.), a molybdenum halide (for example, MoF3, MoCl3, MoBr3, MoI3, etc.), a tungsten halide (for example, WF3, WCl3, WBr3, WI3, etc.), a manganese halide (for example, MnF2, MnCl2, MnBr2, MnI2, etc.), a technetium halide (for example, TcF2, TcCl2, TcBr2, TcI2, etc.), a rhenium halide (for example, ReF2, ReCl2, ReBr2, ReI2, etc.), an iron halide (for example, FeF2, FeCl2, FeBr2, FeI2, etc.), a ruthenium halide (for example, RuF2, RuCl2, RuBr2, RuI2, etc.), an osmium halide (for example, OsF2, OsCl2, OsBr2, OsI2, etc.), a cobalt halide (for example, CoF2, CoCl2, CoBr2, CoI2, etc.), a rhodium halide (for example, RhF2, RhCl2, RhBr2, RhI2, etc.), an iridium halide (for example, IrF2, IrCl2, IrBr2, IrI2, etc.), a nickel halide (for example, NiF2, NiCl2, NiBr2, NiI2, etc.), a palladium halide (for example, PdF2, PdCl2, PdBr2, PdI2, etc.), a platinum halide (for example, PtF2, PtCl2, PtBr2, PtI2, etc.), a copper halide (for example, CuF, CuCl, CuBr, CuI, etc.), a silver halide (for example, AgF, AgCl, AgBr, AgI, etc.), and a gold halide (for example, AuF, AuCl, AuBr, AuI, etc.).
Examples of the post-transition metal halide may include a zinc halide (for example, ZnF2, ZnCl2, ZnBr2, ZnI2, etc.), an indium halide (for example, InI3, etc.), and a tin halide (for example, SnI2, etc.).
Examples of the lanthanide metal halide may include YbF, YbF2, YbF3, SmF3, YbCl, YbCl2, YbCl3, SmCl3, YbBr, YbBr2, YbBr3, SmBr3, YbI, YbI2, YbI3, and SmI3.
Examples of the metalloid halide may include an antimony halide (for example, SbCl5, etc.).
Examples of the metal telluride may include an alkali metal telluride (for example, Li2Te, Na2Te, K2Te, Rb2Te, Cs2Te, etc.), an alkaline earth metal telluride (for example, BeTe, MgTe, CaTe, SrTe, BaTe, etc.), a transition metal telluride (for example, TiTe2, ZrTe2, HfTe2, V2Te3, Nb2Te3, Ta2Te3, Cr2Te3, Mo2Te3, W2Te3, MnTe, TcTe, ReTe, FeTe, RuTe, OsTe, CoTe, RhTe, IrTe, NiTe, PdTe, PtTe, Cu2Te, CuTe, Ag2Te, AgTe, Au2Te, etc.), a post-transition metal telluride (for example, ZnTe, etc.), and a lanthanide metal telluride (for example, LaTe, CeTe, PrTe, NdTe, PmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, etc.).
In an embodiment, when the hole transport layer 120 includes a layer including the p-dopant, an amount of the p-dopant in the layer including the p-dopant may be about 0.1 volume % to about 10 volume %, for example, about 0.5 volume % to about 5 volume %.
A thickness of the layer including the p-dopant may be about 50 Å to about 2,000 Å, for example, about 100 Å to about 1,500 Å.
In
The first electrode 110 may be formed by, for example, applying a material for forming the first electrode 110 onto the substrate by utilizing a deposition or sputtering method. When the first electrode 110 is an anode, the material for forming the first electrode 110 may be a high-work function material.
The first electrode 110 may be a reflective electrode, a semi-transmissive electrode, or a transmissive electrode. To form the first electrode 110 as a transmissive electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), or any combination thereof may be utilized as the material for forming the first electrode 110. In an embodiment, to form the first electrode 110 as a semi-transmissive electrode or a reflective electrode, magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), or any combination thereof may be utilized as the material for forming the first electrode 110.
The first electrode 110 may have a single-layered structure consisting of a single layer, or a multilayer structure including a plurality of layers. For example, the first electrode 110 may have a three-layered structure of ITO/Ag/ITO.
The organic photodetector 10 according to an embodiment may include a charge auxiliary layer that facilitates migration of holes and electrons divided in the activation layer 140.
The charge auxiliary layer may include a hole injection layer and the hole transport layer 120, which facilitate migration of holes, and may include the electron transport layer 160 and an electron injection layer, which facilitate migration of electrons.
Charge auxiliary layers arranged between the first electrode 110 and the activation layer 140 may be collectively referred to as a hole transport region.
The hole transport region may include the hole injection layer, the hole transport layer 120, and the electron blocking layer.
The hole transport region may include a hole transporting material. For example, the hole transporting material may include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof:
In an embodiment, each of Formulae 201 and 202 may include at least one of groups represented by Formulae CY201 to CY217:
In an embodiment, ring CY201 to ring CY204 in Formulae CY201 to CY217 may each independently be a benzene group, a naphthalene group, a phenanthrene group, or an anthracene group.
In an embodiment, each of Formulae 201 and 202 may include at least one of groups represented by Formulae CY201 to CY203.
In an embodiment, Formula 201 may include at least one of groups represented by Formulae CY201 to CY203 and at least one of groups represented by Formulae CY204 to CY217.
In an embodiment, xa1 in Formula 201 may be 1, R201 may be a group represented by one of Formulae CY201 to CY203, xa2 may be 0, and R202 may be a group represented by one of Formulae CY204 to CY207.
In an embodiment, each of Formulae 201 and 202 may not include (e.g., may exclude) groups represented by Formulae CY201 to CY203.
In an embodiment, each of Formulae 201 and 202 may not include (e.g., may exclude) groups represented by Formulae CY201 to CY203, and may include at least one of groups represented by Formulae CY204 to CY217.
In an embodiment, each of Formulae 201 and 202 may not include (e.g., may exclude) groups represented by Formulae CY201 to CY217.
For example, the hole transporting material may include at least one of Compounds HT1 to HT46, m-MTDATA, TDATA, 2-TNATA, NPB(NPD), β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated NPB, TAPC, HMTPD, 4,4′,4″-tris(N-carbazolyl)triphenylamine (TCTA), polyaniline/dodecylbenzenesulfonic acid (PANI/DBSA), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphor sulfonic acid (PANI/CSA), polyaniline/poly(4-styrenesulfonate) (PANI/PSS), or any combination thereof:
A thickness of the hole transport region may be in a range of about 50 Å to about 10,000 Å, for example, about 100 Å to about 4,000 Å. When the hole transport region includes a hole injection layer, a hole transport layer, or any combination thereof, a thickness of the hole injection layer may be in a range of about 100 Å to about 9,000 Å, for example, about 100 Å to about 1,000 Å, and a thickness of the hole transport layer may be in a range of about 50 Å to about 2,000 Å, for example, about 100 Å to about 1,500 Å. When the thicknesses of the hole transport region, the hole injection layer and the hole transport layer are within these ranges, satisfactory hole-transporting characteristics may be obtained without a substantial increase in driving voltage.
The electron blocking layer may prevent or reduce leakage of electrons from the activation layer 140 to the hole transport region. The hole transporting material may be included in the electron transport layer 160 and the electron blocking layer.
Charge auxiliary layers arranged between the activation layer 140 and the second electrode 170 may be collectively referred to as an electron transport region.
The electron transport region may have: i) a single-layered structure consisting of a single layer consisting of a single material, ii) a single-layered structure consisting of a single layer consisting of a plurality of different materials, or iii) a multilayer structure including a plurality of layers including different materials.
The electron transport region may include a buffer layer, a hole blocking layer, the electron transport layer 160, an electron injection layer, or any combination thereof.
For example, the electron transport region may have an electron transport layer/electron injection layer structure, a hole blocking layer/electron transport layer/electron injection layer structure, a buffer layer/electron transport layer/electron injection layer structure, or a buffer layer/electron transport layer structure, wherein, for each structure, constituting layer are sequentially stacked from the activation layer 140.
The electron transport region (for example, the buffer layer, the hole blocking layer, or the electron transport layer 160 in the electron transport region) may include a metal-free compound including at least one TT electron-deficient nitrogen-containing C1-C60 cyclic group.
In an embodiment, the electron transport region may include a compound represented by Formula 601:
[Ar601]xe11—[(L601)xe1—R601]xe21 Formula 601
wherein, in Formula 601,
In an embodiment, when xe11 in Formula 601 is 2 or more, two or more Ar601(s) may be linked to each other via a single bond.
In an embodiment, Ar601 in Formula 601 may be a substituted or unsubstituted anthracene group.
In an embodiment, the electron transport region may include a compound represented by Formula 601-1:
In an embodiment, xe1 and xe611 to xe613 in Formulae 601 and 601-1 may each independently be 0, 1, or 2.
The electron transport region may include at least one of Compounds ET1 to ET45, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP), 4,7-diphenyl-1,10-phenanthroline (Bphen), Alq3, BAlq, TAZ, NTAZ, or any combination thereof:
A thickness of the electron transport region may be about 50 Å to about 5,000 Å, for example, about 100 Å to about 4,000 Å. When the electron transport region includes a buffer layer, a hole blocking layer, an electron transport layer, or any combination thereof, thickness of the buffer layer and the hole blocking layer may each independently be about 20 Å to about 1,000 Å, for example, about 30 Å to about 300 Å, and a thickness of the electron transport layer may be about 100 Å to about 1,000 Å, for example, about 150 Å to about 500 Å. When the thicknesses of the buffer layer, the hole blocking layer, and/or the electron transport layer are within the ranges described above, satisfactory electron-transporting characteristics may be obtained without a substantial increase in driving voltage.
The electron transport region (for example, the electron transport layer in the electron transport region) may further include, in addition to the materials described above, a metal-containing material.
The metal-containing material may include an alkali metal complex, an alkaline earth metal complex, or any combination thereof. A metal ion of the alkali metal complex may be a Li ion, a Na ion, a K ion, a Rb ion, or a Cs ion, and a metal ion of the alkaline earth metal complex may be a Be ion, a Mg ion, a Ca ion, a Sr ion, or a Ba ion. A ligand coordinated with the metal ion of the alkali metal complex or the alkaline earth-metal complex may include a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxyphenyloxadiazole, a hydroxyphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenylbenzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof.
In an embodiment, the metal-containing material may include a Li complex. The Li complex may include, for example, Compound ET-D1 (LiQ) or ET-D2:
The electron transport region may include an electron injection layer that facilitates electron injection. The electron injection layer may be in direct contact with the second electrode 170.
The electron injection layer may have: i) a single-layered structure consisting of a single layer consisting of a single material, ii) a single-layered structure consisting of a single layer consisting of a plurality of different materials, or iii) a multilayer structure including a plurality of layers including different materials.
The electron injection layer may include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth metal complex, a rare earth metal complex, or any combination thereof.
The alkali metal may include Li, Na, K, Rb, Cs, or any combination thereof. The alkaline earth metal may include Mg, Ca, Sr, Ba, or any combination thereof. The rare earth metal may include Sc, Y, Ce, Tb, Yb, Gd, or any combination thereof.
The alkali metal-containing compound, the alkaline earth metal-containing compound, and the rare earth metal-containing compound may include oxides, halides (for example, fluorides, chlorides, bromides, or iodides), or tellurides of the alkali metal, the alkaline earth metal, and the rare earth metal, or any combination thereof.
The alkali metal-containing compound may include alkali metal oxides, such as Li2O, Cs2O, or K2O, alkali metal halides, such as LiF, NaF, CsF, KF, LiI, NaI, CsI, or KI, or any combination thereof. The alkaline earth metal-containing compound may include an alkaline earth metal compound, such as BaO, SrO, CaO, BaxSr1-xO (x is a real number satisfying the condition of 0<x<1), BaxCa1-xO (x is a real number satisfying the condition of 0<x<1), and/or the like. The rare earth metal-containing compound may include YbF3, ScF3, Sc2O3, Y2O3, Ce2O3, GdF3, TbF3, YbI3, ScI3, TbI3, or any combination thereof. In an embodiment, the rare earth metal-containing compound may include lanthanide metal telluride. Examples of the lanthanide metal telluride may include LaTe, CeTe, PrTe, NdTe, PmTe, SmTe, EuTe, GdTe, TbTe, DyTe, HoTe, ErTe, TmTe, YbTe, LuTe, La2Te3, Ce2Te3, Pr2Te3, Nd2Te3, Pm2Te3, Sm2Te3, Eu2Te3, Gd2Te3, Tb2Te3, Dy2Te3, Ho2Te3, Er2Te3, Tm2Te3, Yb2Te3, and Lu2Te3.
The alkali metal complex, the alkaline earth-metal complex, and the rare earth metal complex may include i) one of an ion of the alkali metal, the alkaline earth metal, and the rare earth metal and ii), as a ligand bonded to the metal ion, for example, a hydroxyquinoline, a hydroxyisoquinoline, a hydroxybenzoquinoline, a hydroxyacridine, a hydroxyphenanthridine, a hydroxyphenyloxazole, a hydroxyphenylthiazole, a hydroxyphenyloxadiazole, a hydroxyphenylthiadiazole, a hydroxyphenylpyridine, a hydroxyphenyl benzimidazole, a hydroxyphenylbenzothiazole, a bipyridine, a phenanthroline, a cyclopentadiene, or any combination thereof.
The electron injection layer may include (e.g., consist of) an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal-containing compound, an alkaline earth metal-containing compound, a rare earth metal-containing compound, an alkali metal complex, an alkaline earth metal complex, a rare earth metal complex, or any combination thereof, as described above. In an embodiment, the electron injection layer may further include an organic material (for example, a compound represented by Formula 601).
In an embodiment, the electron injection layer may include (e.g., consist of):
When the electron injection layer further includes an organic material, the alkali metal, alkaline earth metal, rare earth metal, alkali metal-containing compound, alkaline earth metal-containing compound, rare earth metal-containing compound, alkali metal complex, alkaline earth-metal complex, rare earth metal complex, or any combination thereof may be homogeneously or non-homogeneously dispersed in a matrix including the organic material.
A thickness of the electron injection layer may be about 1 Å to about 100 Å, and, for example, about 3 Å to about 90 Å. When the thickness of the electron injection layer is within the range described above, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.
The second electrode 170 may be disposed above the activation layer 140 or the electron transport region as described above. The second electrode 170 may be a cathode. At this time, as a material for forming the second electrode 170, a metal, an alloy, an electrically conductive compound, or any combination thereof, each having a low work function, may be utilized.
The second electrode 170 may include lithium (Li), silver (Ag), magnesium (Mg), aluminum (Al), aluminum-lithium (Al—Li), calcium (Ca), magnesium-indium (Mg—In), magnesium-silver (Mg—Ag), ytterbium (Yb), silver-ytterbium (Ag—Yb), ITO, IZO, or any combination thereof. The second electrode 170 may be a transmissive electrode, a semi-transmissive electrode, or a reflective electrode.
The second electrode 170 may have a single-layered structure or a multilayer structure including a plurality of layers.
A first capping layer may be located outside the first electrode 110, and/or a second capping layer may be located outside the second electrode 170.
The first capping layer and/or the second capping layer may prevent or reduce penetration of impurities, such as water or oxygen, to the organic photodetector 10, thereby improving reliability of the organic photodetector 10.
Each of the first capping layer and second capping layer may include a material having a refractive index (at 589 nm) of 1.6 or more.
The first capping layer and the second capping layer may each independently be an organic capping layer including an organic material, an inorganic capping layer including an inorganic material, or an organic-inorganic composite capping layer including an organic material and an inorganic material.
At least one of the first capping layer or the second capping layer may each independently include carbocyclic compounds, heterocyclic compounds, amine group-containing compounds, porphyrin derivatives, phthalocyanine derivatives, naphthalocyanine derivatives, alkali metal complexes, alkaline earth metal complexes, or any combination thereof. The carbocyclic compound, the heterocyclic compound, and the amine group-containing compound may be optionally substituted with a substituent containing O, N, S, Se, Si, F, Cl, Br, I, or any combination thereof. In an embodiment, at least one of the first capping layer or the second capping layer may each independently include an amine group-containing compound.
In an embodiment, at least one of the first capping layer or the second capping layer may each independently include a compound represented by Formula 201, a compound represented by Formula 202, or any combination thereof.
In an embodiment, at least one of the first capping layer or the second capping layer may each independently include at least one of Compounds HT28 to HT33, at least one of Compounds CP1 to CP6, β-NPB, or any combination thereof:
There may be provided an electronic apparatus including the organic photodetector as described above. In an embodiment, the electronic apparatus may further include a light-emitting device.
Accordingly, the electronic apparatus according to an embodiment includes: a substrate including a photodetection area and an emission area;
The hole transport region and the electron transport region may each be the same as described above.
For example, the hole transport layer, the optical auxiliary layer, the buffer layer, the electron transport layer, and the opposite electrode may be arranged throughout the photodetection area and the emission area.
The electronic apparatus may be applied to one or more suitable displays, light sources, lighting, personal computers (for example, a mobile personal computer), mobile phones, digital cameras, electronic diaries, electronic dictionaries, electronic game machines, medical instruments (for example, electronic thermometers, sphygmomanometers, blood glucose meters, pulse measurement devices, pulse wave measurement devices, electrocardiogram displays, ultrasonic diagnostic devices, or endoscope displays), fish finders, one or more suitable measuring instruments, meters (for example, meters for a vehicle, an aircraft, and a vessel), projectors, and/or the like.
Referring to
The substrate 601 and the substrate 602 may be a flexible substrate, a glass substrate, or a metal substrate. A buffer layer and a thin-film transistor may be disposed on the substrate 601.
The buffer layer may prevent or reduce penetration of impurities through the substrate 601 and provide a flat surface on the substrate 601. The thin-film transistor may be disposed on the buffer layer and may include an activation layer, a gate electrode, a source electrode, and a drain electrode.
Such a thin-film transistor may be electrically connected to the light-emitting device 500 to drive the light-emitting device 500. One of the source electrode and drain electrode may be electrically connected to a second pixel electrode 510 of the light-emitting device 500.
Another thin-film transistor may be electrically connected to the organic photodetector 400. One of the source electrode or the drain electrode may be electrically connected to a first pixel electrode 410 of the organic photodetector 400.
The organic photodetector 400 may include the first pixel electrode 410, a hole transport layer 411, a first optical auxiliary layer 420, a second optical auxiliary layer 432, an activation layer 440, a buffer layer 450, an electron transport layer 460, and an opposite electrode 470.
In an embodiment, the first pixel electrode 410 may be an anode, and the opposite electrode 470 may be a cathode. In other words, as the organic photodetector 400 is driven by applying a reverse bias between the first pixel electrode 410 and the opposite electrode 470, the electronic apparatus 100 may detect light incident onto the organic photodetector 400, generate charges, and extract the charges as a current.
The light-emitting device 500 may include the second pixel electrode 510, the hole transport layer 411, the first optical auxiliary layer 420, the second optical auxiliary layer 432, an emission layer 540, the buffer layer 450, the electron transport layer 460, and the opposite electrode 470.
In an embodiment, the second pixel electrode 510 may be an anode, and the opposite electrode 470 may be a cathode. In other words, in the light-emitting device 500, holes injected from the second pixel electrode 510 and electrons injected from the opposite electrode 470 recombine in the emission layer 540 to generate excitons, which generate light by changing from an excited state to a ground state.
The first pixel electrode 410 and the second pixel electrode 510 may each be the same as described in connection with the first electrode 110 in the present specification.
A pixel-defining film 405 may be formed at edge portions of the first pixel electrode 410 and the second pixel electrode 510. The pixel-defining film 405 may define a pixel area and may electrically insulate the first pixel electrode 410 and the second pixel electrode 510. The pixel-defining film 405 may include, for example, one or more suitable organic insulating materials (e.g., a silicon-based material), inorganic insulating materials, or organic/inorganic composite insulating materials. The pixel-defining film 405 may be a transmissive film that transmits visible light or a blocking film that blocks visible light.
The hole transport layer 411 and the optical auxiliary layer, which are common layers, are formed sequentially on the first pixel electrode 410 and the second pixel electrode 510. The hole transport layer 411 and the optical auxiliary layer may each be the same as described in the present specification.
The activation layer 440 is formed above the second optical auxiliary layer 432 in correspondence with the photodetection area. The activation layer 440 is the same as described in the present specification.
The emission layer 540 is formed above the second optical auxiliary layer 432 in correspondence with the emission area. In an embodiment, the light-emitting device 500 may further include, between the second pixel electrode 510 and the emission layer 540, an electron blocking layer arranged in correspondence with the emission area.
As common layers for the entirety of the photodetection area and a first emission area, the buffer layer 450, the electron transport layer 460, and the opposite electrode 470 are sequentially formed above the activation layer 440 and the emission layer 540. The buffer layer 450, the electron transport layer 460, and the opposite electrode 470 may each be the same as described in connection with the buffer layer, the electron transport layer, and the second electrode 170 in the present specification.
Each of the hole transport layer 411, the first optical auxiliary layer 420, the second optical auxiliary layer 432, the buffer layer 450, and the electron transport layer 460 may be arranged throughout the photodetection area and the emission area.
As such, in the electronic apparatus 100, because a common layer is arranged in the organic photodetector 400 and the light-emitting device 500, a manufacturing process may be reduced, and a functional layer material utilized in the light-emitting device 500 may also be utilized in the organic photodetector 400 such that the organic photodetector 400 may be arranged in-pixel in the electronic apparatus 100.
In an embodiment, an electron injection layer may be further included between the electron transport layer 460 and the opposite electrode 470.
A capping layer may be disposed on the opposite electrode 470. A material for forming the capping layer may include the organic material and/or the inorganic material described herein. The capping layer may serve to protect the organic photodetector 400 and the light-emitting device 500 and to assist effective emission of light generated from the light-emitting device 500.
An encapsulation portion 490 may be disposed on the capping layer. The encapsulation portion 490 may be disposed on the organic photodetector 400 and the light-emitting device 500 to protect the organic photodetector 400 and the light-emitting device 500 from water or oxygen. The encapsulation portion 490 may include: an inorganic film including silicon nitride (SiNx), silicon oxide (SiOx), indium tin oxide, indium zinc oxide, or any combination thereof; an organic film including polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyethylene sulfonate, polyoxy methylene, poly aryllate, hexamethyl disiloxane, an acrylic resin (e.g., polymethyl methacrylate, polyacrylic acid, and/or the like), an epoxy-based resin (e.g., aliphatic glycidyl ether (AGE) and/or the like), or any combination thereof; or a combination of the inorganic film and the organic film.
The electronic apparatus 100 may be, for example, a display apparatus. The electronic apparatus 100 includes both (e.g., simultaneously) the organic photodetector 400 and the light-emitting device 500, and thus, may be a display apparatus with a light detection function.
In
Elements illustrated in
The first light-emitting device 501 may include a second pixel electrode 511, the hole transport layer 411, the first optical auxiliary layer 420, the second optical auxiliary layer 432, a first emission layer 541, the buffer layer 450, the electron transport layer 460, and the opposite electrode 470.
The second light-emitting device 502 may include a third pixel electrode 512, the hole transport layer 411, the first optical auxiliary layer 420, the second optical auxiliary layer 432, a second emission layer 542, the buffer layer 450, the electron transport layer 460, and the opposite electrode 470.
The third light-emitting device 503 may include a fourth pixel electrode 513, the hole transport layer 411, the first optical auxiliary layer 420, the second optical auxiliary layer 432, a third emission layer 543, the buffer layer 450, the electron transport layer 460, and the opposite electrode 470.
The second pixel electrode 511, the third pixel electrode 512, and the fourth pixel electrode 513 may be arranged in correspondence with a first emission area, a second emission area, and a third emission area, respectively, and may each be the same as described in connection with the first electrode 110 in the present specification.
The first emission layer 541 may be arranged in correspondence with the first emission area and emit first color light, the second emission layer 542 may be arranged in correspondence with the second emission area and emit second color light, and the third emission layer 543 may be arranged in correspondence with the third emission area and emit third color light.
A maximum emission wavelength of the first color light, a maximum emission wavelength of the second color light, and a maximum emission wavelength of the third color light may be identical to or different from each other. For example, a maximum emission wavelength of the first color light and a maximum emission wavelength of the second color light may each be longer than a maximum emission wavelength of the third color light.
For example, the first color light may be red light, the second color light may be green light, and the third color light may be blue light, but embodiments are not limited thereto. Therefore, the electronic apparatus 100a may be capable of full-color emission. When a mixed light of the first color light, the second color light, and the third color light is white light, the first color light, the second color light, and the third color light may not be respectively limited to red light, green light, and blue light.
The organic photodetector 400, the first light-emitting device 501, the second light-emitting device 502, and the third light-emitting device 503 may each be a sub-pixel forming a pixel. In an embodiment, one pixel may include at least one organic photodetector 400.
The electronic apparatus 100a may be a display apparatus. Because the electronic apparatus 100a may include the organic photodetector 400, the first light-emitting device 501, the second light-emitting device 502, and the third light-emitting device 503, the electronic apparatus 100a may be a full-color display apparatus having a light detection function.
In the electronic apparatus 100a shown in
For example, red light, green light, and blue light may respectively be emitted from the first light-emitting device 501, the second light-emitting device 502, and the third light-emitting device 503.
The electronic apparatus 100a according to an embodiment may have a function of detecting an object being in contact with the electronic apparatus 100a, for example, a fingerprint of a finger. For example, as shown in
In an embodiment, as shown in
The layers constituting the hole transport region, the activation layer, and the layers constituting the electron transport region may be formed in a specific region by utilizing one or more suitable methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB) deposition, ink-jet printing, laser printing, and/or laser-induced thermal imaging (LITI).
When layers constituting the hole transport region, an activation layer, and layers constituting the electron transport region may each independently be formed by vacuum-deposition, the vacuum-deposition may be performed at a deposition temperature in a range of about 100° C. to about 500° C., at a vacuum degree in a range of about 10−8 torr to about 10−3 torr, and at a deposition rate in a range of about 0.01 Å/sec to about 100 Å/sec, depending on a material to be included in each layer and a structure of each layer to be formed.
The term “C3-C60 carbocyclic group” as utilized herein refers to a cyclic group consisting of carbon only as a ring-forming atom and having three to sixty carbon atoms, and the term “C1-C60 heterocyclic group” as utilized herein refers to a cyclic group that has one to sixty carbon atoms and further has, in addition to carbon, a heteroatom as a ring-forming atom. The C3-C60 carbocyclic group and the C1-C60 heterocyclic group may each be a monocyclic group consisting of one ring or a polycyclic group in which two or more rings are condensed with each other. In an embodiment, the C1-C60 heterocyclic group has 3 to 61 ring-forming atoms.
The term “cyclic group” as utilized herein may include the C3-C60 carbocyclic group and the C1-C60 heterocyclic group.
The term “π electron-rich C3-C60 cyclic group” as utilized herein refers to a cyclic group that has three to sixty carbon atoms and does not include *—N═*′ as a ring-forming moiety, and the term “π electron-deficient nitrogen-containing C1-C60 cyclic group” as utilized herein refers to a heterocyclic group that has one to sixty carbon atoms and includes *—N═*′ as a ring-forming moiety.
In an embodiment,
The term “cyclic group”, “C3-C60 carbocyclic group”, “C1-C60 heterocyclic group”, “π electron-rich C3-C60 cyclic group”, or “π electron-deficient nitrogen-containing C1-C60 cyclic group” as utilized herein refers to a group condensed to any cyclic group or a polyvalent group (for example, a divalent group, a trivalent group, a tetravalent group, etc.), depending on the structure of a formula in connection with which the terms are utilized. In an embodiment, “a benzene group” may be a benzo group, a phenyl group, a phenylene group, and/or the like, which may be easily understood by those of ordinary skill in the art according to the structure of a formula including the “benzene group.”
Depending on context, a divalent group may refer or be a polyvalent group (e.g., trivalent, tetravalent, etc., and not just divalent) per, e.g., the structure of a formula in connection with which of the terms are utilized.
For example, examples of a monovalent C3-C60 carbocyclic group and a monovalent C1-C60 heterocyclic group may include a C3-C10 cycloalkyl group, a C1-C10 heterocycloalkyl group, a C3-C10 cycloalkenyl group, a C1-C10 heterocycloalkenyl group, a C6-C60 aryl group, a C1-C60 heteroaryl group, a monovalent non-aromatic condensed polycyclic group, and a monovalent non-aromatic condensed heteropolycyclic group, and examples of a divalent C3-C60 carbocyclic group and a divalent C1-C60 heterocyclic group may include a C3-C10 cycloalkylene group, a C1-C10 heterocycloalkylene group, a C3-C10 cycloalkenylene group, a C1-C10 heterocycloalkenylene group, a C6-C60 arylene group, a C1-C60 heteroarylene group, a divalent non-aromatic condensed polycyclic group, and a divalent non-aromatic condensed heteropolycyclic group.
The term “C1-C60 alkyl group” as utilized herein refers to a linear or branched aliphatic hydrocarbon monovalent group that has one to sixty carbon atoms, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a tert-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a sec-isopentyl group, an n-hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, an n-heptyl group, an isoheptyl group, a sec-heptyl group, a tert-heptyl group, an n-octyl group, an isooctyl group, a sec-octyl group, a tert-octyl group, an n-nonyl group, an isononyl group, a sec-nonyl group, a tert-nonyl group, an n-decyl group, an isodecyl group, a sec-decyl group, and a tert-decyl group. The term “C1-C60 alkylene group” as utilized herein refers to a divalent group having the same structure as the C1-C60 alkyl group.
The term “C2-C60 alkenyl group” as utilized herein refers to a monovalent hydrocarbon group having at least one carbon-carbon double bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethenyl group, a propenyl group, and a butenyl group. The term “C2-C60 alkenylene group” as utilized herein refers to a divalent group having the same structure as the C2-C60 alkenyl group.
The term “C2-C60 alkynyl group” as utilized herein refers to a monovalent hydrocarbon group having at least one carbon-carbon triple bond in the middle or at the terminus of the C2-C60 alkyl group, and examples thereof include an ethynyl group and a propynyl group. The term “C2-C60 alkynylene group” as utilized herein refers to a divalent group having the same structure as the C2-C60 alkynyl group.
The term “C1-C60 alkoxy group” as utilized herein refers to a monovalent group represented by —OA101 (wherein A101 is the C1-C60 alkyl group), and examples thereof include a methoxy group, an ethoxy group, and an isopropyloxy group.
The term “C3-C10 cycloalkyl group” as utilized herein refers to a monovalent saturated hydrocarbon cyclic group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, an adamantyl group, a norbornyl group (or a bicyclo[2.2.1]heptyl group), a bicyclo[1.1.1]pentyl group, a bicyclo[2.1.1 ]hexyl group, and a bicyclo[2.2.2]octyl group. The term “C3-C10 cycloalkylene group” as utilized herein refers to a divalent group having the same structure as the C3-C10 cycloalkyl group.
The term “C1-C10 heterocycloalkyl group” as utilized herein refers to a monovalent cyclic group that further includes, in addition to a carbon atom, at least one heteroatom as a ring-forming atom and has 1 to 10 carbon atoms, and examples thereof include a 1,2,3,4-oxatriazolidinyl group, a tetrahydrofuranyl group, and a tetrahydrothiophenyl group. The term “C1-C10 heterocycloalkylene group” as utilized herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkyl group.
The term “C3-C10 cycloalkenyl group” utilized herein refers to a monovalent cyclic group that has three to ten carbon atoms and at least one carbon-carbon double bond in the ring thereof and no aromaticity, and examples thereof include a cyclopentenyl group, a cyclohexenyl group, and a cycloheptenyl group. The term “C3-C10 cycloalkenylene group” as utilized herein refers to a divalent group having the same structure as the C3-C10 cycloalkenyl group.
The term “C1-C10 heterocycloalkenyl group” as utilized herein refers to a monovalent cyclic group that has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom, 1 to 10 carbon atoms, and at least one carbon-carbon double bond in the cyclic structure thereof. Examples of the C1-C10 heterocycloalkenyl group include a 4,5-dihydro-1,2,3,4-oxatriazolyl group, a 2,3-dihydrofuranyl group, and a 2,3-dihydrothiophenyl group. The term “C1-C10 heterocycloalkenylene group” as utilized herein refers to a divalent group having the same structure as the C1-C10 heterocycloalkenyl group.
The term “C6-C60 aryl group” as utilized herein refers to a monovalent group having a carbocyclic aromatic system having six to sixty carbon atoms, and the term “C6-C60 arylene group” as utilized herein refers to a divalent group having a carbocyclic aromatic system having six to sixty carbon atoms. Examples of the C6-C60 aryl group include a phenyl group, a pentalenyl group, a naphthyl group, an azulenyl group, an indacenyl group, an acenaphthyl group, a phenalenyl group, a phenanthrenyl group, an anthracenyl group, a fluoranthenyl group, a triphenylenyl group, a pyrenyl group, a chrysenyl group, a perylenyl group, a pentaphenyl group, a heptalenyl group, a naphthacenyl group, a picenyl group, a hexacenyl group, a pentacenyl group, a rubicenyl group, a coronenyl group, and an ovalenyl group. When the C6-C60 aryl group and the C6-C60 arylene group each include two or more rings, the rings may be condensed with each other.
The term “C1-C60 heteroaryl group” as utilized herein refers to a monovalent group having a heterocyclic aromatic system that has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom, and 1 to 60 carbon atoms. The term “C1-C60 heteroarylene group” as utilized herein refers to a divalent group having a heterocyclic aromatic system that has, in addition to a carbon atom, at least one heteroatom as a ring-forming atom, and 1 to 60 carbon atoms. Examples of the C1-C60 heteroaryl group include a pyridinyl group, a pyrimidinyl group, a pyrazinyl group, a pyridazinyl group, a triazinyl group, a quinolinyl group, a benzoquinolinyl group, an isoquinolinyl group, a benzoisoquinolinyl group, a quinoxalinyl group, a benzoquinoxalinyl group, a quinazolinyl group, a benzoquinazolinyl group, a cinnolinyl group, a phenanthrolinyl group, a phthalazinyl group, and a naphthyridinyl group. When the C1-C60 heteroaryl group and the C1-C60 heteroarylene group each include two or more rings, the rings may be condensed with each other.
The term “monovalent non-aromatic condensed polycyclic group” as utilized herein refers to a monovalent group having two or more rings condensed with each other, only carbon atoms (for example, having 8 to 60 carbon atoms) as ring-forming atoms, and non-aromaticity in its molecular structure when considered as a whole. Examples of the monovalent non-aromatic condensed polycyclic group include an indenyl group, a fluorenyl group, a spiro-bifluorenyl group, a benzofluorenyl group, an indenophenanthrenyl group, and an indeno anthracenyl group. The term “divalent non-aromatic condensed polycyclic group” as utilized herein refers to a divalent group having the same structure as a monovalent non-aromatic condensed polycyclic group.
The term “monovalent non-aromatic condensed heteropolycyclic group” as utilized herein refers to a monovalent group having two or more rings condensed with each other, at least one heteroatom, in addition to carbon atoms (for example, including 1 to 60 carbon atoms), as a ring-forming atom, and non-aromaticity in its molecular structure when considered as a whole. Examples of the monovalent non-aromatic condensed heteropolycyclic group include a 9,9-dihydroacridinyl group and a 9H-xanthenyl group. The term “divalent non-aromatic condensed heteropolycyclic group” as utilized herein refers to a divalent group having the same structure as a monovalent non-aromatic condensed heteropolycyclic group.
The term “C6-C60 aryloxy group” as utilized herein indicates —OA102 (wherein A102 is the C6-C60 aryl group), and the term “C6-C60 arylthio group” as utilized herein indicates —SA103 (wherein A103 is the C6-C60 aryl group).
The term “C7-C60 arylalkyl group” as utilized herein refers to —A104A105 (where A104 may be a C1-C54 alkylene group, and A105 may be a C6-C59 aryl group), and the term “C2-C60 heteroarylalkyl group” utilized herein refers to —A106A107 (where A106 may be a C1-C59 alkylene group, and A107 may be a C1-C59 heteroaryl group). R10a may be:
Q1 to Q3, Q11 to Q13, Q21 to Q23, and Q31 to Q33 may each independently be: hydrogen; deuterium; —F; —Cl; —Br; —I; a hydroxyl group; a cyano group; a nitro group; a C1-C60 alkyl group; a C2-C60 alkenyl group; a C2-C60 alkynyl group; a C1-C60 alkoxy group; or a C3-C60 carbocyclic group, a C1-C60 heterocyclic group, a C7-C60 aryl alkyl group, or a C2-C60 heteroaryl alkyl group, each unsubstituted or substituted with deuterium, —F, a cyano group, a C1-C60 alkyl group, a C1-C60 alkoxy group, a phenyl group, a biphenyl group, or any combination thereof.
The term “hetero atom” as utilized herein refers to any atom other than a carbon atom. Examples of the heteroatom include O, S, N, P, Si, B, Ge, Se, or any combination thereof.
The term “the third-row transition metal” as utilized herein includes hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), and/or the like.
The term “Ph” as utilized herein refers to a phenyl group, the term “Me” as utilized herein refers to a methyl group, the term “Et” as utilized herein refers to an ethyl group, the term “ter-Bu” or “But” as utilized herein refers to a tert-butyl group, and the term “OMe” as utilized herein refers to a methoxy group.
The term “biphenyl group” as utilized herein refers to “a phenyl group that is substituted with a phenyl group.” In other words, the “biphenyl group” is a substituted phenyl group having a C6-C60 aryl group as a substituent.
The term “terphenyl group” as utilized herein refers to “a phenyl group that is substituted with a biphenyl group”. The “terphenyl group” is a substituted phenyl group having, as a substituent, a C6-C60 aryl group that is substituted with a C6-C60 aryl group.
An ITO glass substrate (anode) was cut to a size of 50 mm×50 mm×0.5 mm, sonicated in isopropyl alcohol and pure water for 10 minutes in each solvent, and cleaned by irradiation of ultraviolet rays and exposure of ozone thereto for 10 minutes. Then, the glass substrate was mounted to a vacuum-deposition apparatus. HT3 was vacuum-deposited on the anode to form a hole transport layer having a thickness of 1,250 Å.
Compound D and p-dopant HAT-CN were co-deposited on the hole transport layer to form a first optical auxiliary layer having a thickness of 100 Å (doping concentration: 1 volume %), and then Compound D was deposited thereon to form a second optical auxiliary layer having a thickness of 100 Å.
SubPC having a thickness of 200 Å and a C60 fullerene having a thickness of 250 Å were sequentially deposited on the second optical auxiliary layer to form an activation layer.
Next, BAlq was vacuum-deposited thereon to form a buffer layer having a thickness of 50 Å, and ET1 was vacuum-deposited on the buffer layer to form an electron transport layer having a thickness of 300 Å.
LiF was vacuum-deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and then MgAg having a thickness of 100 Å was sequentially deposited thereon to form a cathode, thereby completing manufacture of an organic photodetector.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 1, except that Compound D was deposited on the hole transport layer to form a single optical auxiliary layer having a thickness of 200 Å.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 1, except that Compound E was deposited on the hole transport layer to form a single optical auxiliary layer having a thickness of 200 Å.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 1, except that Compound F was deposited on the hole transport layer to form a single optical auxiliary layer having a thickness of 200 Å.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 1, except that Compound E (HOMO energy value=−5.15 eV) was deposited on the hole transport layer to form a first optical auxiliary layer having a thickness of 100 Å, and then Compound F (HOMO energy value=−5.30 eV) was deposited thereon to form a second optical auxiliary layer having a thickness of 100 Å.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 1, except that Compound F (HOMO energy value=−5.30 eV) was deposited on the hole transport layer to form a first optical auxiliary layer having a thickness of 100 Å, and then Compound E (HOMO energy value=−5.15 eV) was deposited thereon to form a second optical auxiliary layer having a thickness of 100 Å.
An ITO glass substrate (anode) was cut to a size of 50 mm×50 mm×0.5 mm, sonicated in isopropyl alcohol and pure water for 10 minutes in each solvent, and cleaned by irradiation of ultraviolet rays and exposure of ozone thereto for 10 minutes. Then, the glass substrate was mounted to a vacuum-deposition apparatus. HT3 was vacuum-deposited on the anode to form a hole transport layer having a thickness of 1,250 Å.
Compound D and p-dopant HAT-CN were co-deposited on the hole transport layer to form a first optical auxiliary layer having a thickness of 100 Å (doping concentration: 1 volume %), and then Compound D was deposited thereon to form a second optical auxiliary layer having a thickness of 100 Å.
Compound A was deposited on the second optical auxiliary layer to a thickness of 200 Å, and then Compounds B and C were co-deposited thereon (at a weight ratio of 5:5) to a thickness of 250 Å, to thereby form an activation layer.
Next, BAlq was vacuum-deposited thereon to form a buffer layer having a thickness of 50 Å, and ET1 was vacuum-deposited on the buffer layer to form an electron transport layer having a thickness of 300 Å.
LiF was vacuum-deposited on the electron transport layer to form an electron injection layer having a thickness of 10 Å, and then MgAg having a thickness of 100 Å was sequentially deposited thereon to form a cathode, thereby completing manufacture of an organic photodetector.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 6, except that Compound D was deposited on the hole transport layer to form a single optical auxiliary layer having a thickness of 200 Å.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 6, except that Compound E was deposited on the hole transport layer to form a single optical auxiliary layer having a thickness of 200 Å.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 6, except that Compound F was deposited on the hole transport layer to form a single optical auxiliary layer having a thickness of 200 Å.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 6, except that Compound E (HOMO energy value=−5.15 eV) was deposited on the hole transport layer to form a first optical auxiliary layer having a thickness of 100 Å, and then Compound F (HOMO energy value=−5.30 eV) was deposited thereon to form a second optical auxiliary layer having a thickness of 100 Å.
An organic photodetector was manufactured in substantially the same manner as in Comparative Example 6, except that Compound F (HOMO energy value=−5.30 eV) was deposited on the hole transport layer to form a first optical auxiliary layer having a thickness of 100 Å, and then Compound E (HOMO energy value=−5.15 eV) was deposited thereon to form a second optical auxiliary layer having a thickness of 100 Å.
External quantum efficiency (EQE) at a wavelength of 530 nm, which is a peak wavelength of each of the organic photodetectors manufactured in Comparative Examples 1 to 10 and Examples 1 and 2, was measured, and results thereof are shown in Table 1.
Referring to Table 1, it was found that in substantially the same device structure, Example 1 exhibited better external quantum efficiency than Comparative Examples 2 to 5, and Example 2 exhibited better external quantum efficiency than Comparative Examples 7 to 10.
Regarding only the organic photodetector, Comparative Example 1 exhibited better efficiency than Example 1, but the organic photodetector of Comparative Example 1 had a lateral leakage issue occurring between an OLED pixel and an OPD pixel.
As a result of manufacturing electronic apparatuses with Comparative Example 1 and Example 1, each including a green organic light-emitting device as shown in
Likewise, regarding only the organic photodetector, Comparative Example 6 exhibited better efficiency than Example 2, but the organic photodetector of
Comparative Example 6 had a lateral leakage issue occurring between an OLED pixel and an OPD pixel. As a result of manufacturing electronic apparatuses with Comparative Example 6 and Example 2, each including a green organic light-emitting device as shown in
The organic photodetector according to an embodiment has excellent or suitable efficiency.
The apparatus, device and/or any other relevant devices or components according to embodiments of the present invention described herein may be implemented utilizing any suitable hardware, firmware (e.g. an application-specific integrated circuit), software, or a combination of software, firmware, and hardware. For example, the various components of the apparatus may be formed on one integrated circuit (IC) chip or on separate IC chips. Further, the various components of the apparatus may be implemented on a flexible printed circuit film, a tape carrier package (TCP), a printed circuit board (PCB), or formed on one substrate. Further, the various components of the apparatus may be a process or thread, running on one or more processors, in one or more computing devices, executing computer program instructions and interacting with other system components for performing the various functionalities described herein. The computer program instructions are stored in a memory which may be implemented in a computing device using a standard memory device, such as, for example, a random access memory (RAM). The computer program instructions may also be stored in other non-transitory computer readable media such as, for example, a CD-ROM, flash drive, or the like. Also, a person of skill in the art should recognize that the functionality of various computing devices may be combined or integrated into a single computing device, or the functionality of a particular computing device may be distributed across one or more other computing devices without departing from the scope of the exemplary embodiments of the present invention.
It should be understood that embodiments described herein should be considered in a descriptive sense only and not for purposes of limitation. Descriptions of features or aspects within each embodiment should typically be considered as available for other similar features or aspects in other embodiments. While one or more embodiments have been described with reference to the drawings, it will be understood by those of ordinary skill in the art that one or more suitable changes in form and details may be made therein without departing from the spirit and scope as defined by the following claims and equivalents thereof.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2022-0165100 | Nov 2022 | KR | national |
