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JP-7857078-B2 - Near-infrared absorbing materials, near-infrared absorbing/blocking films, and photoelectric elements, as well as organic sensors and electronic devices.

JP7857078B2JP 7857078 B2JP7857078 B2JP 7857078B2JP-7857078-B2

Inventors

  • 崔 惠 成
  • 權 五 逵
  • 金 煌 スク
  • 李 光 熙
  • 林 東 ソク

Assignees

  • 三星電子株式会社

Dates

Publication Date
20260512
Application Date
20201124
Priority Date
20191122

Claims (20)

  1. It is a near-infrared absorbing material, A near-infrared absorbing material characterized by containing a compound represented by the chemical formula 1 shown below. (In the above chemical formula 1, Ar is a benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted tetracene ring, or a substituted or unsubstituted pyrene ring. X1 is S, Se, Te, S(=O), or S(=O) 2 , X2 is O, S, Se, Te, CR x - CR y , CR xx - CR yy , or S (=O) (where R x and R y are independently hydrogen, deuterium, a C1-C30 alkyl group, a C1-C30 haloalkyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, a C3-C30 heteroaryl group, a halogen, a cyano group, or a combination thereof, and R xx and R yy are linked to each other to form an aromatic ring or a heteroaromatic ring). Ar1 and Ar2 are each independently S- containing heteroarenes. Ar1 and Ar2 are either the same or different, and are selected from the chemical formulas C-1-1 to C-1-3 shown below. Ar3 and Ar4 are, independently, substituted or unsubstituted arenes with 6 to 30 carbon atoms, substituted or unsubstituted heteroarenes with 3 to 30 carbon atoms, or fused rings thereof. R1 and R2 are independently hydrogen, deuterium, halogen, cyano group, nitro group, hydroxyl group, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted C6-C10 aryl group, or substituted or unsubstituted C3-C10 heteroaryl group. L1 and L2 are single bonds, In the aforementioned chemical formulas C-1-1 to C-1-3, Each aromatic ring's hydrogen can be substituted with a halogen, a cyano group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C1-C30 haloalkyl group, -SiH3 , a C1-C30 alkylsilyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, or a C3-C30 heteroaryl group. Y1 is S, S (=O), or S(=O ) 2 , Y2 is O, S, Se, Te, S(=O), S(=O) 2 , NR a2 , SiR b2 R c2 , GeR d2 R e2 , or CR f2 R g2 (where R a2 , R b2 , R c2 , R d2 , R e2 , R f2 , and R g2 are independently hydrogen, a C1-C10 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkoxy group, -SiH3 , a C1-C10 alkylsilyl group, and -NH3 ). (A C1-C10 alkylamine group, a C6-C10 arylamine group, a C6-C14 aryl group, a C6-C14 aryloxy group, a C3-C12 heteroaryl group, a halogen, a cyano group, or a combination thereof ) R b2 and R c2 , R d2 and R e2 , and R f2 and R g2 either exist independently or are bonded to each other to form a spiro ring. At least one * located outside the aromatic ring is a linkage site with Ar of chemical formula 1, and at least one * located inside the aromatic ring is a linkage site with the N( R1 )-containing ring containing R1 of chemical formula 1, and the N( R2 )-containing ring of chemical formula 1 containing R2 .
  2. The near-infrared absorbing material according to claim 1, characterized in that Ar in the chemical formula 1 is one of the moieties represented by the chemical formula group A-1 shown below. (Among the chemical formula group A-1 above, Each aromatic ring's hydrogen can be replaced with a halogen, a cyano group, a C1-C10 alkyl group, a C1-C10 alkoxy group, a C1-C10 haloalkyl group, a silyl group, or a C1-C10 alkylsilyl group. The asterisk (*) inside the aromatic ring is the part that bonds with the -N-X 1 -N- containing ring and the -N=X 2 =N- containing ring of chemical formula 1. The asterisks (*) on the left and right linking groups are the parts that connect to Ar1 and Ar2 in chemical formula 1.
  3. The near-infrared absorbing material according to claim 1, characterized in that, in the chemical formula 1, when X2 is CR xx - CR yy , the aromatic ring formed by the linkage of R xx and R yy is a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted acenaphthene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted tetracene ring, or a substituted or unsubstituted pyrene ring.
  4. The near-infrared absorbing material according to claim 1, characterized in that, in the chemical formula 1, when X2 is CR xx - CR yy , the aromatic ring formed by linking R xx and R yy to each other is a substituted or unsubstituted quinoline ring, a substituted or unsubstituted isoquinoline ring, a substituted or unsubstituted quinoxaline ring, a substituted or unsubstituted quinazoline ring, a substituted or unsubstituted phenanthroline ring, a substituted or unsubstituted pyrimidine ring, or a substituted or unsubstituted benzodithiophene ring.
  5. The near-infrared absorbing material according to claim 1, characterized in that, in the chemical formula 1, when X2 is CR xx - CR yy , the aromatic ring formed by the linkage of R xx and R yy is one of the moieties represented by the chemical formula group B-1 shown below. (Among the above chemical formula group B-1, Each aromatic ring's hydrogen can be substituted with a halogen, a cyano group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C1-C30 haloalkyl group, -SiH3 , a C1-C30 alkylsilyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, or a C3-C30 heteroaryl group. The asterisk (*) inside the aromatic ring represents the part that bonds with the carbon in CR xx - CR yy .
  6. The near-infrared absorbing material according to claim 1, characterized in that, in the chemical formula 1, when X2 is CR xx - CR yy , the aromatic ring formed by the linkage of R xx and R yy is one of the moieties represented by the chemical formula group B-2 shown below. (Among the chemical formula group B-2 above, Each aromatic ring's hydrogen can be substituted with a halogen, a cyano group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C1-C30 haloalkyl group, -SiH3 , a C1-C30 alkylsilyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, or a C3-C30 heteroaryl group. The asterisk (*) inside the aromatic ring represents the part that bonds with the carbon in CR xx - CR yy .
  7. The near-infrared absorbing material according to claim 1, characterized in that, in the chemical formula 1, when X2 is CR xx - CR yy , the aromatic ring formed by the linkage of R xx and R yy is one of the moieties represented by the following chemical formulas B-3-1 or B-3-2. (In the above chemical formulas B-3-1 and B-3-2, Ar 11 and Ar 12 are independently selected from substituted or unsubstituted arenes with 6 to 30 carbon atoms and substituted or unsubstituted heteroarenes with 3 to 30 carbon atoms. In chemical formula B-3-1, Z1 and Z2 are independently CR a or N (where Ra is hydrogen, deuterium, a C1-C30 alkyl group, a C1-C30 haloalkyl group, -SiH3 , a C1-C30 alkylsilyl group, -NH2 , a C1-C30 alkylamine group, a C6-C30 arylamine group, a C6-C30 aryl group, a C6-C30 aryloxy group, a C3-C30 heteroaryl group, a halogen, a cyano group, or a combination thereof). Each aromatic ring's hydrogen can be substituted with a halogen, a cyano group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C1-C30 haloalkyl group, -SiH3 , a C1-C30 alkylsilyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, or a C3-C30 heteroaryl group. The asterisk (*) inside the aromatic ring represents the part that bonds with the carbon in CR xx - CR yy .
  8. The near-infrared absorbing material according to claim 7, characterized in that the moiety represented by the chemical formula B-3-1 is represented by the chemical formula group B-3-11 shown below, and the moiety represented by the chemical formula B-3-2 is represented by the chemical formula group B-3-21 shown below. (Among the above chemical formula group B-3-11, Each aromatic ring's hydrogen can be substituted with a halogen, a cyano group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C1-C30 haloalkyl group, -SiH3 , a C1-C30 alkylsilyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, or a C3-C30 heteroaryl group. The asterisk (*) inside the aromatic ring represents the part that bonds with the carbon in CR xx - CR yy . (Among the chemical formulas in group B-3-21 above, Each aromatic ring's hydrogen can be substituted with a halogen, a cyano group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C1-C30 haloalkyl group, -SiH3 , a C1-C30 alkylsilyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, or a C3-C30 heteroaryl group. X a and X b are each independently selected from O, S, Se, Te, NR a , SiR b R c , and GeR d Re (where R a , R b , R c , R d , and Re are each independently selected from hydrogen, halogen, cyano group, substituted or unsubstituted C1-C30 alkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C6-C30 aryl group, and substituted or unsubstituted C6-C30 aryloxy group). The asterisk (*) inside the aromatic ring represents the part that bonds with the carbon in CR xx - CR yy .
  9. It is a near-infrared absorbing material, It contains the compound represented by the chemical formula 1 shown below, A near-infrared absorbing material characterized in that, in the aforementioned chemical formula 1, Ar 1 and Ar 2 are either the same or different, and are selected from the following chemical formulas C-5-1 to C-5-8. (In the above chemical formula 1, Ar is a benzene ring, a substituted or unsubstituted naphthalene ring, a substituted or unsubstituted anthracene ring, a substituted or unsubstituted phenanthrene ring, a substituted or unsubstituted tetracene ring, or a substituted or unsubstituted pyrene ring. X1 is S, Se, Te, S(=O), or S(=O) 2 , X2 is O, S, Se, Te, CR x - CR y , CR xx - CR yy , or S (=O) (where R x and R y are independently hydrogen, deuterium, a C1-C30 alkyl group, a C1-C30 haloalkyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, a C3-C30 heteroaryl group, a halogen, a cyano group, or a combination thereof, and R xx and R yy are linked to each other to form an aromatic ring or a heteroaromatic ring). Ar3 and Ar4 are, independently, substituted or unsubstituted arenes with 6 to 30 carbon atoms, substituted or unsubstituted heteroarenes with 3 to 30 carbon atoms, or fused rings thereof. R1 and R2 are independently hydrogen, deuterium, halogen, cyano group, nitro group, hydroxyl group, substituted or unsubstituted C1-C10 alkyl group, substituted or unsubstituted C1-C10 alkoxy group, substituted or unsubstituted C6-C10 aryl group, or substituted or unsubstituted C3-C10 heteroaryl group. L1 and L2 are single bonds, (Among the chemical formulas C-5-1 to C-5-8 mentioned above, Each aromatic ring's hydrogen can be substituted with a halogen, a cyano group, a C1-C30 alkyl group, a C1-C30 alkoxy group, a C1-C30 haloalkyl group, -SiH3 , a C1-C30 alkylsilyl group, a C6-C30 aryl group, a C6-C30 aryloxy group, or a C3-C30 heteroaryl group. Y1 is O, S, Se, Te, S(=O), S(=O) 2 , NR a1 , SiR b1 R c1 , or GeR d1 Re e1 (where R a1 , R b1 , R c1 , R d1 , and Re e1 are independently hydrogen, a C1-C10 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkoxy group, -SiH3 , a C1-C10 alkylsilyl group, -NH3 , a C1-C10 alkylamine group, a C6-C10 arylamine group, a C6-C14 aryl group, a C6-C14 aryloxy group, a C3-C12 heteroaryl group, a halogen, a cyano group, or a combination thereof). Y2 and Y3 are independently O, S, Se, Te, S(=O), S(=O) 2 , NR a2 , SiR b2 R c2 , GeR d2 R e2 , or CR f2 R g2 (where R a2 , R b2 , R c2 , R d2 , R e2 , R f2 , and R g2 are independently hydrogen, a C1-C10 alkyl group, a C1-C10 haloalkyl group, a C1-C10 alkoxy group, -SiH3 , a C1-C10 alkylsilyl group, and -NH3 ) (These include alkylamine groups having 1 to 10 carbon atoms, arylamine groups having 6 to 10 carbon atoms, aryl groups having 6 to 14 carbon atoms, aryloxy groups having 6 to 14 carbon atoms, heteroaryl groups having 3 to 12 carbon atoms, halogens, cyano groups, or combinations thereof.) R b1 and R c1 , R d1 and R e1 , R b2 and R c2 , R d2 and R e2 , and R f2 and R g2 each exist independently or are bonded to each other to form a spiro ring. At least one * located outside the aromatic ring is a linkage site with Ar of chemical formula 1, and at least one * located inside the aromatic ring is a linkage site with the N( R1 )-containing ring containing R1 of chemical formula 1, and the N( R2 )-containing ring of chemical formula 1 containing R2 .
  10. It is a near-infrared absorbing material, A near-infrared absorbing material characterized by containing compounds represented by the following chemical formulas 1-1 to 1-9.
  11. The near-infrared absorbing material according to claim 1, characterized in that its peak absorption wavelength belongs to the wavelength range of 750 nm to 3000 nm.
  12. A near-infrared absorbing/blocking film characterized by containing a near-infrared absorbing material according to any one of claims 1 to 10.
  13. A photoelectric element, The first electrode and the second electrode are facing each other, It comprises an active layer disposed between the first electrode and the second electrode, The photoelectric element is characterized in that the active layer includes a near-infrared absorbing material according to any one of claims 1 to 10.
  14. The photoelectric element according to claim 13, characterized in that the active layer further comprises a fullerene or a fullerene derivative.
  15. The photoelectric element according to claim 13, characterized in that the peak absorption wavelength of the active layer belongs to the wavelength region of 750 nm to 3000 nm.
  16. The first electrode and the second electrode are facing each other, An active layer disposed between the first electrode and the second electrode, The device has at least one charge auxiliary layer between the active layer and the first electrode or between the active layer and the second electrode, The photoelectric element is characterized in that the charge auxiliary layer includes an infrared absorbing material according to any one of claims 1 to 10.
  17. The photoelectric element according to claim 16, characterized in that the active layer further comprises the near-infrared absorbing material.
  18. It is an organic sensor, An organic sensor characterized by including a photoelectric element according to any one of claims 13 to 17.
  19. Semiconductor substrate and A first photoelectric element present on the semiconductor substrate selectively absorbs light in the first near-infrared wavelength region, The system includes an additional sensor that selectively absorbs light in a separate wavelength region different from the first near-infrared wavelength region, The first photoelectric element is characterized by containing a near-infrared absorbing material according to any one of claims 1 to 10.
  20. The additional sensor is an infrared sensor at least partially embedded in a semiconductor substrate, and the separate wavelength region is a separate near-infrared wavelength region different from the first near-infrared wavelength region. The organic sensor according to claim 19, characterized in that the first photoelectric element and the infrared sensor are superimposed in a direction perpendicular to the upper surface of the semiconductor substrate.

Description

This invention relates to near-infrared (NIR) absorbing materials, near-infrared absorbing/blocking films, photoelectric elements, and organic sensors and electronic devices, and more particularly to near-infrared absorbing materials, near-infrared absorbing/blocking films, photoelectric elements, and organic sensors and electronic devices exhibiting excellent near-infrared absorption characteristics. Digital cameras and camcorders use image sensors to capture images and store them as electrical signals. These image sensors include a sensor that decomposes incident light by wavelength and converts each component into an electrical signal. In recent years, the development of near-infrared absorbing materials with excellent absorption characteristics in the near-infrared region, as well as photoelectric elements or organic sensors containing them, has become a challenge in order to improve the sensitivity of sensors in low-light environments and to use sensors as biorecognition devices. Japanese Patent Publication No. 2009-205029 This is a cross-sectional view showing the schematic configuration of a photoelectric element according to one embodiment of the present invention.This is a cross-sectional view showing a schematic configuration of a photoelectric element according to another embodiment of the present invention.This is a cross-sectional view showing the schematic configuration of an organic sensor according to one embodiment of the present invention.This is a cross-sectional view showing a schematic configuration of an organic sensor according to another embodiment of the present invention.This is a cross-sectional view showing a schematic configuration of an organic sensor according to another embodiment of the present invention.This is a schematic diagram showing an example of a pixel array of an organic sensor according to one embodiment of the present invention.This is a cross-sectional view showing the schematic configuration of an organic sensor according to one embodiment of the present invention.This is a cross-sectional view showing a schematic configuration of an organic sensor according to another embodiment of the present invention.This is a cross-sectional view showing a schematic configuration of an organic sensor according to another embodiment of the present invention.This is a cross-sectional view showing a schematic configuration of an organic sensor according to another embodiment of the present invention.This is a cross-sectional view showing a schematic configuration of an organic sensor according to another embodiment of the present invention.This is a block diagram illustrating the schematic configuration of a digital camera including an organic sensor according to one embodiment of the present invention.This is a block diagram illustrating an outline of an electronic device according to one embodiment of the present invention.This graph shows the results of measuring the photoelectric conversion efficiency of photoelectric elements in Example 1 and Comparative Example 4. Next, specific examples of embodiments for implementing the near-infrared absorbing material, near-infrared absorbing/blocking film, photoelectric element, organic sensor, and electronic device according to the present invention will be described with reference to the drawings. However, the structures that are actually applied can be realized in a variety of different forms and are not limited to the embodiments described herein. The thickness was enlarged in the drawing to clearly represent various layers and regions. When a part of a layer, membrane, region, or plate is said to be "on top" of another part, this includes not only when it is "directly above" the other part, but also when there is another part in between. Conversely, when one part is said to be "directly above" another part, it means that there is no other part in between. When one component is said to be "on top" of another, this can mean that it is in contact with the top or bottom of the other component. In this specification, a component and/or its physical properties may be referred to as “identical” or “equivalent” to another component, and in this specification, a component and/or its physical properties may be referred to as “identical” to another component, meaning that they are “the same,” “equivalent,” “substantially identical,” or “substantially equivalent.” The phrase "substantially identical" or "substantially equivalent" to other components and/or their physical properties can be understood as including components and properties that are identical or equivalent to other components and/or their physical properties within the limits of manufacturing tolerances and/or material tolerances. Other components and their properties that are identical or substantially identical may mean that components and/or their properties are structurally identical or substantially identical, functionally identical or substantially identical, and/or co