Source: http://www.google.es/patents/US9118019
Timestamp: 2017-11-23 02:16:17
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Matched Legal Cases: ['Application No. 06005687', 'Application No. 06005687', 'art 2', 'Application No. 2005', 'Application No. 07723467', 'Application No. 2007', 'Application No. 10', 'Application No. 2009', 'Application No. 2009']

Patente US9118019 - Heterocyclic radical or diradical, the dimers, oligomers, polymers, dispiro ... - Google Patentes
The present invention relates to heterocyclic radicals or diradicals, the dimers, oligomers, polymers, dispiro compounds and polycycles thereof, to the use thereof, to organic semiconductive materials and to electronic and optoelectronic components....http://www.google.es/patents/US9118019?utm_source=gb-gplus-sharePatente US9118019 - Heterocyclic radical or diradical, the dimers, oligomers, polymers, dispiro compounds and polycycles thereof, the use thereof, organic semiconductive material and electronic or optoelectronic component
Número de publicación US9118019 B2
Número de solicitud US 13/398,162
También publicado como CN101093874A, CN101093874B, CN101134744A, CN101134744B, CN101405884A, CN101405884B, DE502006000749D1, EP1837926A1, EP1837926B1, US8134146, US20070252140, US20120146012
Número de publicación 13398162, 398162, US 9118019 B2, US 9118019B2, US-B2-9118019, US9118019 B2, US9118019B2
Inventores Michael Limmert, Olaf Zeika, Martin Amman, Horst Hartmann, Ansgar Werner
Citas de patentes (81), Otras citas (182), Clasificaciones (12)
US 9118019 B2
The present invention relates to heterocyclic radicals or diradicals, the dimers, oligomers, polymers, dispiro compounds and polycycles thereof, to the use thereof, to organic semiconductive materials and to electronic and optoelectronic components.
1. A heterocyclic compound, or a dimer, oligomer, polymer, dispiro compound, or polycycle thereof, having a structure according to one of the following formulae:
wherein at least one of A1 and A2 are present; and A1 and A2, independently, are cyclic linkages that form a ring system selected from the group consisting of, substituted or unsubstituted, carbocyclic, heterocyclic, and polycyclic ring systems; and wherein T is selected from CR22, CR22R23, N, NR21, O, or S; or
wherein structure 7 has one or more bridge bonds Z, Z1, and Z2, and wherein Z, Z1 and Z2 are independently selected from alkyl, alkenyl, alkynyl, cycloalkyl, sililyl, alkylsililyl, diazo, disulphide, heterocycloalkyl, heterocyclyl, piperazinyl, dialkyl ether, polyether, primary alkylamine, arylamine, polyamine, aryl, or heteroaryl;
wherein X and Y are independently selected from O, S, N, NR21, P, or PR21; wherein R1-2 and R21-23 are independently selected from, substituted or unsubstituted, aryl, heteroaryl, heterocyclyl, diarylamine, diheteroarylamine, dialkylamine, heteroarylalkylamine, arylalkylamine, H, F, cycloalkyl, halocycloalkyl, heterocycloalkyl, alkyl, alkenyl, alkynyl, trialkylsilyl, triarylsilyl, halogen, styryl, alkoxy, aryloxy, thioalkoxy, thioaryloxy, sililyl, trialkylsilylalkynyl, (hetero)aliphatic ring system, or (hetero)aromatic ring system, wherein the (hetero)aliphatic or (hetero)aromatic ring system comprises one or more of R1-2 and R21-23.
2. The heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 1, wherein A1 and A2 are independently selected from, substituted or unsubstituted, aromatic or heteroaromatic ring systems.
3. The heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 2, wherein the aromatic or heteroaromatic ring systems are independently selected from benzo, naphtho, thiophene, furan, thiazole, imidazole, oxazole, thiadiazole, pyrazine, thiopyran, dithiine, phthalic acid imide, or dithiazole radicals.
4. The heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 3, wherein at least one of the benzo, naphtho, thiophene, furan, thiazole, imidazole, oxazole, thiadiazole, pyrazine, thiopyran, dithiine, phthalic acid imide, or dithiazole radicals are substituted with one or more substituents selected from R1-2 and R21-23.
5. The heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 1, wherein Z, Z1, and Z2 are selected from piperazinyl, alkyl, or cycloalkyl.
6. The heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 1 having one of the following structures:
wherein X1 and Y1 are independently selected from N or P, and wherein R3-18 are independently selected from, substituted or unsubstituted, aryl, heteroaryl, heterocyclyl, diarylamine, diheteroarylamine, dialkylamine, heteroarylalkylamine, arylalkylamine, H, F, cycloalkyl, halocycloalkyl, heterocycloalkyl, alkyl, alkenyl, alkynyl, trialkylsilyl, triarylsilyl, halogen, styryl, alkoxy, aryloxy, thioalkoxy, thioaryloxy, sililyl, trialkylsilylalkynyl, (hetero)aliphatic ring system, or (hetero)aromatic ring system, wherein the (hetero)aliphatic or (hetero)aromatic ring system comprises one or more of R3-18 and R21-23.
7. The heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 1, wherein R1-2 and R21-23 are individually selected from, substituted or unsubstituted, phenyl, biphenyl, naphthyl, anthranyl, thienyl, imidazolyl, pyrrolyl, thiazolyl, oxazolyl, thiadiazolyl, piperidyl, pyrrolidyl, morpholyl, or thiomorpholyl.
8. The heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 1, wherein R1-2 and R21-23 are independently selected from alkyl, cycloalkyl, dialkylamine, diarylamine, alkoxy, aryloxy, thioaryl, thioalkoxy, or perfluoroalkyl.
9. The heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 1, wherein the polycycle is a tricycle.
10. An electronic or optoelectronic component comprising the heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 1, wherein the heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof is a dopant for doping an organic semiconductive matrix material, a blocking layer, a charge injection layer, an electrode material, a memory material, or a semiconductor layer itself in the electronic and optoelectronic component.
11. An organic semiconductive material comprising at least one organic matrix material and the heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof according to claim 1, wherein the heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof is a dopant.
12. The organic semiconductive material according to claim 11, wherein the molar doping ratio of dopant to matrix molecule or the doping ratio of dopant to monomeric units of a polymeric matrix molecule is between 1:1 and 1:100,000.
13. An electronic or optoelectronic component comprising an electronically functionally active area, wherein the electronically active area comprises a heterocyclic compound, or a dimer, oligomer, polymer, dispiro compound, or polycycle thereof, having a structure according to one of the following formulae:
wherein X and Y are independently selected from O, S, N, NR21, P, or PR21; wherein R1-2 and R21 are independently selected from, substituted or unsubstituted, aryl, heteroaryl, heterocyclyl, diarylamine, diheteroarylamine, dialkylamine, heteroarylalkylamine, arylalkylamine, H, F, cycloalkyl, halocycloalkyl, heterocycloalkyl, alkyl, alkenyl, alkynyl, trialkylsilyl, triarylsilyl, halogen, styryl, alkoxy, aryloxy, thioalkoxy, thioaryloxy, sililyl, trialkylsilylalkynyl, (hetero)aliphatic ring system, or (hetero)aromatic ring system, wherein the (hetero)aliphatic or (hetero)aromatic ring system comprises one or more of R1-2 and R21-23.
14. The electronic or optoelectronic component according to claim 13, wherein the electronically active area comprises an organic semiconductive matrix material and a dopant, wherein the dopant modifies the electronic properties of the semiconductive matrix material, and the dopant comprises the heterocyclic compound, or the dimer, oligomer, polymer, dispiro compound, or polycycle thereof.
15. The electronic or optoelectronic component according to claim 13, wherein the electronic or optoelectronic component is an organic light-emitting diode, a photovoltaic cell, an organic solar cell, an organic diode, an organic field effect transistor, or a photoinitiated and magnetic memory.
This application is a division of U.S. patent application Ser. No. 11/688,777, now U.S. Patent No. 8,134,146,filed Mar. 20, 2007,which claims priority to European Patent Application No. 06005687.6,filed Mar. 21, 2006.The disclosures of U.S. patent application Ser. No. 11/688,777 and European Patent Application No. 06005687.6 are incorporated herein by reference.
The object of the present invention is to provide novel compounds which can he used as n-dopants, as an injection layer or as a blocking layer, wherein the compounds also have sufficiently low oxidation potentials for producing electron transport materials for organic light-emitting diodes, without having any disruptive effect on the matrix material, and are intended to provide an effective increase in the number of charge carriers in the matrix material and are relatively easy to handle.
These objects and others are achieved by heterocyclic radicals or diradicals, the dimers, oligomers, polymers, dispiro compounds and polycycles thereof, having structures according to the following formulae:
wherein structure 7 has one or more bridge bonds Z and/or Z1 and/or Z2, and Z, Z1 and Z2 may independently be selected from alkyl, alkenyl, alkynyl, cycloalkyl, sililyl; alkylsililyl, diazo, disulphide, heterocycloalkyl, heterocyclyl, piperazinyl, dialkyl ether, polyether, primary alkylamine, arylamine and polyamine, aryl and heteroaryl;
wherein in structures 8a-8c the ring size of each heterocycle may vary from 5-7 atoms;
wherein X, Y═O, S, N, NR21, P or PR21; R0-19, R21, R22 and R23 are independently selected from, substituted or unsubstituted, aryl, heteroaryl, heterocyclyl, diarylamine, diheteroarylamine, dialkylamine, heteroarylalkylamine, arylalkylamine, H, F cycloalkyl, halocycloalkyl, heterocycloalkyl, alkyl, alkenyl, alkynyl, trialkylsilyl, triarylsilyl, halogen, styryl, alkoxy, aryloxy, thioalkoxy, thioaryloxy, sililyl and trialkylsilylalkynyl, or R0-19, R21, R22 and R23, alone or in combination, form part of a (hetero)aliphatic or (hetero)aromatic ring system.
R0, R1-R12 in structures 5e-5o and 3h can be chosen from the definition for the R's given in claim 1.
Further, structure 5c is preferred with R1-R16═H or R1, R4-R16═H and R2, R3═CH3. Additionally a particularly preferred compound is based on structure 1a with Y═NR21 with R21=alkyl, preferably methyl; with R0, R21=alkyl, preferably methyl; R1, R2=aryl, especially phenyl, tolyl, xylyl, anisyl, thienyl, furanyl, alkyl, especially cyclohexyl, cyclopentyl, n-alkyl; or mixed variations with R1=alkyl, especially methyl, ethyl, propyl, and R2=aryl, especially phenyl, tolyl, xylyl, anisyl, thienyl, furanyl.
Within the context of the present invention, the term “dimers” is understood to mean compounds which occur by reacting two monoradicals or diradicals with each other.
The term “oligomers” is understood to mean compounds which are composed of a plurality of diradicals, wherein a first radical end of a diradical reacts with a first end of a further diradical and a second end of the newly formed, larger diradical in turn reacts with a second further diradical. The ends of such oligomers can be reacted with monoradicals. The term “polymer” is understood to mean compounds which, compared to oligomers, are composed of a larger number of diradicals.
A “dispiro compound” is according to the present invention an intramolecular addition product of a diradical, the radical centers of which are separated by a structural element of that kind, that said structural element connects the radical bearing carbon atoms, i.e. the carbon atoms which add to each other.
The term “polycycle” is meant to comprise an intramolecular addition product of a diradical, the radical centers of which are separated by a structural element of that kind that said structural element connects at least one other carbon atom than the ones bearing radicals (e.g. at least one atom in alpha position).
In the present application, a dopant is understood to mean on the one hand a material which is mixed in (“the layer is doped with the dopant”). On the other hand, the dopant may be the redox-active species which brings about charge transfer conductivity (“the dopant brings about n-doping”). It is assumed that the dimers, etc. are dopants of the first type, whereas the corresponding radicals are dopants of the second type.
It is also conceivable to use the compounds according to the invention as radical scavengers or antioxidants in food chemistry, pharmacy, in fire-fighting or as pesticides, in particular as an insecticide, herbicide, fungicide or the like. The use as radical initiators for radical reactions (preferably radically induced polymerisations or living radical polymerisations) is also conceivable. Finally, it should he mentioned that triplet diradicals can also be used as a magnetic compound in the form of memory or switch structures in organic electronic and optoelectronic components.
1 . The dimer/oligomer/polymer/dispiro compound or polycycle itself absorbs electromagnetic radiation of suitable wavelength and is thereby cleaved into the doping radicals or diradicals. An electron is transferred from the HOMO of the radical/diradical to the LUMO of the matrix material.
2 . The matrix material is excited by exposure to electromagnetic radiation, so that an electron from the HOMO of the dopant (dimer/oligomer/polymer/dispiro compound/polycycle) is transferred to the former HOMO, which is now single-occupied. The dopant then undergoes an irreversible reaction.
3 . The dopant (dimer/oligomer/polymer/dispiro compound/polycycle) is excited photochemically, then an electron transfer takes place from the single-occupied LUMO of the dopant to the LUMO of the matrix material. The dopant then undergoes an irreversible reaction.
However, it is also possible for various mechanisms to occur at the same time, and finally the electron transfer may be brought about by means of a different mechanism not mentioned here, for example by means of thermal splitting of the bond. Once the electromagnetic radiation, source has been switched off, however, all or part of the conductivity is irreversibly and permanently retained.
The radicals, diradicals and derivatives thereof according to the invention can he synthesised by known methods. It will be understood that the cited literature is mentioned only by way of example.
Benzimidazoles c can inter alia be easily synthesised from o-phenylenediamine a and appropriate carboxylic acid derivatives (M. R. DeLuca, S. M. Kerwin Tetrahedron 1997, 53 457-64) or aldehydes (M. Curini et al. Synlett 2004, 10, 1832-4). See also: M. R. Grimmett “Imidazole and Benzimidazole Synthesis” Academic Press; Harcourt Brace & Company, Publishers, London, San Diego, New York, Boston. o-Phenylenediamines are commercially available or can be obtained for example by the method of Suschitsky et al. (J. Chem. Soc. Chem. Comm. 1977, 189-90). Benzothia derivatives or oxazole derivatives can be obtained in the same way via o-mercapto- or o-hydroxyanilines. The alkylation of the N-atom(s) in the heterocyclic five-membered rings c takes place with dimethyl sulphate or diethyl sulphate in the presence of bases (H. Quasi, E. Schmitt Chem. Ber. 1968, 101, 4012-14) or with alkyl halides. The corresponding cationic products (heteroarenium compounds) d can be isolated in neutral form e.g. as perchlorate, tetrafluoroborate, halide, tetraphenylborate or hexafluorophosphate or with other suitable counterions.
Said radicals can be prepared chemically by means of alkali metals or electrochemically or photochemically from the corresponding heteroaromatic cations by reduction (T. Muramatsu et al. Chemistry Letters 1996, 151-2; Pragst et al. J. Electroanal. Chem. 1984, 180, 141-56, J. Heinze, H. Baumgärtel, Ber. Bunsenges. 1972 76/2 94).
Bis-[3-methyl-2-alkyl-1,2-dihydrobenzothiazolyl-(2)] and bis-[3-methyl-2-aryl-1,2-dihydrobenzothiazolyl-(2)] compounds can be obtained directly via benzothiazolium salts and suitable Grignard compounds/A. Kinya; S. Hiroaki; I. Naoki; Bull. Chem. Soc. Japan 1979 52/1, 156-9.
EXAMPLE 1 2-Methylmercapto-1,3-dimethylbenzimidazolium perchlorate
Suspend 0.1 mol of 2-mercaptobenzimidazole in 70 ml of water. Add 0.3 mol of NaHCO3 and 0.5 mol of dimethyl sulphate and stir Overnight at room temperature. 12 ml of 50% tetrafluoroboric acid are added dropwise to the clear solution, which is cooled and the precipitate is removed by suction and recrystallized from 1,2-dichlorethane.
Fp.=160-3° C.
EXAMPLE 2 2-Piperidyl-1,3-dimethylbenzimidazolium perchlorate
Heat 0.01 mol of 2-methylmercapto-1,3-dimethylbenzimidazolium perchlorate with 0.01 mol of piperidine for 4th at reflux in 250 ml of dioxane. Remove the solids by suction and recrystallise from ethanol.
Fp. 179° C.
EXAMPLE 3 2-Dimethylaminobenzimidazolium chloride
Stir 0.05 mol of o-phenylenediaminium dichloride and 0,05 mol of dichloromethylene-N,N-dimethylimmonium chloride in 100 ml of dioxane at room temperature for 12 h. Then heat at reflux for 2.5-3 h, remove the solids by suction and wash with ether. Recrystallise from ethanol.
Fp. 293° C.
EXAMPLE 4 1,4-Bis-1′,1″,3′,3″-tetramethylbenzimidazolium-2′,2″-butane
Suspend 0.01 mol of 1,4-bisbenzimidazolyl-2′,2″-butane in 30 ml of a mixture consisting of 50% water and 50% glycol monomethyl ether, add 0.06 mol of sodium hydrogen carbonate and 0.05 mol dimethyl sulphate and stir overnight at room temperature. Then filter and precipitate with 10 ml of concentrated perchloric acid.
EXAMPLE 5 2,3,5,6-Tetrahydro-1H,4H-3a,10b-diaza-6a-azoniafluoranthene
Heat 0.1 mol of 2-aminobenzimidazole with 0.2 mol of 1,3-dibromopropane and 0.3 mol of KCO3 in 250 ml of DMF for 8 h at 120° C. Remove the solids by suction and fully concentrate the solvent and take up in methanol and then add 70% perchloric acid. Wash the precipitated white crystals with methanol, water and again with methanol.
Fp.: 242° C.
EXAMPLE 6 2-Isopropyl-1,3-dimethylimidazolium perchlorate
Suspend 0.1 mol of 2-mercaptobenzimidazole in 70 ml of water. Add 0.3 mol of NaHCO3 and 0.5 mol of dimethyl sulphate and stir overnight at room temperature. 10 ml of 70% perchloric acid are added dropwise to the clear solution, which is cooled and the precipitate is removed by suction and recrystallized from ethanol.
Fp.=346° C.
EXAMPLE 7 Bis-(N,N′,2,2′-tetramethyl-1H-benzimidazolylium)-1,3-propane diiodide
Suspend 0.02 mol of NaH under argon in 20 ml of dimethoxyethane and add 0.02 mol of 2-methylbenzimidazole under ice cooling. Once evolution of gases is complete, continue stirring for a further 60 min at room temperature and add dropwise 0.01 mol of 1,3-dibromopropane and stir for 10 min. Heat the reaction mixture at 60° C. on the water bath for 4.5 h, stir overnight at room temperature and pour onto ice/water. Remove the precipitated raw product by suction and dry in vacuo. Place 0.005 mol of this intermediate product in 30 ml of water, add 0.015 mol of NaHCO3 and 0.015 mol of dimethyl sulphate, stir overnight and precipitate with 1-2 ml of concentrated hydriodic acid.
Fp.: decomp.>306° C.
EXAMPLE 8 1,2,3,5,6,7-Hexamethylbenzo-1,7-dihydrobenzo[1,2-d,4,5-d′]diimidazolium diperchlorate
Suspend 0.013 mol of 2,6-dimethylbenzo-1,7-dihydrobenzo[1,2-d,4,5-d′]diimidazole in approx, 40-50 ml of water and add 0.078 mol of NaHCO3 and 0,064 mol of dimethyl sulphate. Stir for 12 h at room temperature and add dropwise 4-5 ml of 70% perchloric acid. Remove the white precipitate by suction and wash with ethanol, water and again with ethanol.
Fp.: >350° C.
EXAMPLE a Bis-[1,3-dimethyl-2-N-piperidinyl-1,2-dihydrobenzimidazolyl-(2)]
Heat at reflux 0.01 mol of 2-N-piperidinyl-1,3-dimethylbenzimidazolium tetrafluoroborate with potassium in THF, filter, concentrate and cool. Remove the precipitated crystals by suction and wash with cold acetonitrile.
Fp.: 195° C.
EXAMPLE b Bis-[1,3-dimethyl-2-isopropyl-1,2-dihydrobenzimidazolyl-(2)]
Dissolve 1,3-dimethyl-2-isopropylbenzimidazolium perchlorate in 0.1 M tetrabutylammonium perchlorate in acetonitrile and precipitate in a three-chamber electrolysis cell at −2.3 V using a mercury electrode. The white precipitate is removed by suction, washed with acetonitrile and dried in vacuo.
Fp.: 146° C.
EXAMPLE c Bis-[1,3-dimethyl-2-N-pyrrolidyl-1,2-dihydrobenzimidazolyl-(2)]
Dissolve 1,3-dimethyl-2-N-pyrrolidylbenzimidazolium perchlorate in 0.1 M tetrabutylammonium perchlorate/DMF and precipitate in a three-chamber electrolysis cell at −2.3 V using a mercury electrode. The white precipitate is removed by suction, washed with acetonitrile and dried in vacuo.
Fp.: 120° C.
EXAMPLE d Bis-[1,3,5,6-tetramethyl-2-isopropyl-1,2-dihydrobenzimidazolyl-(2)]
Heat at reflux 0.01 mol of 1,3,5,6-tetramethyl-2-isopropylbenzimidazolium tetrafluoroborate with potassium in THF, filter, concentrate and cool. Remove the precipitated crystals by suction and wash with cold acetonitrile.
Fp.: 129-30° C.
EXAMPLE e 2-Isopropyl-1,3-dimethyl-2,3,6,7-tetrahydro-1H-5,8-dioxa-1,3-diazacyclopenta[b]naphthene
Dissolve 0.1 M tetrabutylammonium perchlorate/acetonitrile and precipitate in a three-chamber electrolysis cell at −2.4 V using a mercury electrode. The white precipitate is removed by suction, washed with acetonitrile and dried in vacuo.
Fp.: 142° C.
EXAMPLE f 1,2,3,5,6,7-Hexamethylbenzo-1,7-dihydrobenzo[1,2-d,4,5-d′]diimidazolyl-(2)oligomeric diradical
Dissolve 0.01 mol of 1,2,3,5,6,7-hexamethylbenzo-1,7-dihydrobenzo[1,2-d,4,5-d′]-diimidazolium diperchlorate in 0.1 M tetrabutylammonium perchlorate/DMF and precipitate in a three-chamber electrolysis cell at −2.3 V using a mercury electrode. The white precipitate is removed by suction, washed with acetonitrile and dried in vacuo.
Fp.: >250° C.
EXAMPLE g Bis-[1,3-dimethyl-2-isopropyl-1,2,4,5,6,7-hexahydrobenzimidazolyl-(2)]
Dissolve 1,3-dimethyl-2-isopropyl-4,5,6,7-tetrahydrobenzimidazolium hexafluorophosphate in 0.1 M tetrabutylammonium hexafluorophosphate in DMF and precipitate in a three-chamber electrolysis cell at −2.6 V using a mercury electrode. The white precipitate is removed by suction, washed with acetonitrile and dried in vacuo.
Fp.: 127-9° C.
EXAMPLE h Bis-[4,5-diphenyl-2-isopropyl-1,2-dihydroimidazolyl-(2)]
Dissolve 4,5-diphenyl-2-isopropylimidazolium hexafluorophosphate in 0.1 M tetrabutylammonium hexafluorophosphate in DMF and precipitate in a three-chamber electrolysis cell at −2.45 V using a mercury electrode. The white precipitate is removed by suction, washed with acetonitrile and dried in vacuo.
Fp.: 160-3° C.
EXAMPLE i Bis-[3-benzyl-2-isopropyl-1,2-dihydrobenzothiazolyl-(2)]
Dissolve 3-benzyl-2-isopropylbenzothiazolium perchlorate in 0.1 M tetrabutylammonium perchlorate in acetonitrile and precipitate in a three-chamber electrolysis cell at −2.3 V using a mercury electrode. The white precipitate is removed by suction, washed with acetonitrile and dried in vacuo.
As n-dopable matrix materials, use may be made inter alia of quinolinato complexes, for example of aluminium or of other main group metals, wherein the quinolinato ligand may also be substituted. In particular, the matrix material may be tris(8-hydroxyquinolinato)aluminium. Other aluminium complexes with O and/or N donor atoms may also optionally be used. Common matrix materials are also zinc phthalocyanine (ZnPc) or zinc tetraphenylporphyrin (ZnTPP), to name just a few examples of phthalocyanine or porphyrin complexes.
As the matrix material, it is also possible to use heteroatoms, such as in particular triazoles, possibly also pyrroles, imidazoles, triazoles, pyridines, pyrimidines, pyridazines, quinoxalines, pyrazino-quinoxalines and the like. The heteroatoms are preferably substituted, in particular aryl-substituted, for example phenyl- or naphthyl-substituted. In particular, the following triazole can be used as matrix material. Further matrix materials can be found for example in A. P. Kulkami et al., Chem. Mater. 16, 4556ff. (2004).
The doping of the respective matrix material with the compounds according to the invention may be carried out by one or a combination of the following methods:
a) Mixed vapour deposition in vacuo with one source for the matrix material and one for the dopant.
b) Sequential deposition of the matrix material and of the n-dopant onto a substrate with subsequent inward diffusion of the dopant, in particular by means of a heat treatment.
c) Doping of a matrix layer with a solution of n-dopant, followed by evaporation of the solvent, in particular by means of a heat treatment.
d) Surface-doping of a matrix material layer by means of a layer of dopant applied to the surface.
e) Preparation of a solution of matrix molecules and dopant and subsequent production of a layer consisting of this solution by means of conventional methods such as evaporation of the solvent or spin coating.
The doping may also take place in such a way that the dopant is evaporated out of a precursor compound, which releases the dopant when heated and/or exposed to radiation. As the precursor compound, it is possible to use for example a carbonyl compound, dinitrogen compound or the like which gives off CO, nitrogen or the like when releasing the dopant, wherein it is also possible to use other suitable precursors, such as salts, e.g. halides, hydrogenated compounds or the like. The exposure to radiation may take place by means of electromagnetic radiation, in particular visible light, UV light or IR light, for example laser light, or else by means of other types of radiation. The exposure to radiation may substantially provide the heat required for evaporation, and it is also possible to introduce the radiation in a targeted manner into certain bands of the compounds or precursors or compound complexes to be evaporated, such as charge transfer complexes, in order to facilitate the evaporation of the compounds by dissociating the complexes for example by transferring them into excited states. However, the complex may in particular also be sufficiently stable to be evaporated without dissociation or to be applied to the substrate under the given conditions. It will be understood that other suitable methods can also be used to carry out the doping.
DOPING USE EXAMPLES
A radical according to the invention or the oligomer, preferably dimer, thereof and diradicals or dispiro compounds and tricycles thereof are provided.
The neutral dimer bis-[1,3-diethyl-2-methyl-1,2-dihydrobenzimidazolyl-(2)] was used together with the matrix material zinc phthalocyanine ZnPc. Doped layers with a doping ratio dopant:matrix material of 1:20 were produced by mixed vapour deposition of matrix and dopant with ZnPc as matrix material. The conductivity here is 3×10−4 S/cm.
In a manner analogous to Example I, mixed vapour deposition of bis-[1,3-dimethyl-2-isopropyl-1,2-dihydrobenzimidazolyl-(2)] and ZnPc was carried out in the ratio as given in example I. The resulting conductivity was 10−3 S/cm.
In a manner analogous to Example I, mixed vapour deposition of bis-[1,3-dimethyl-2-isopropyl-1,2-dihydrobenzimidazolyl-(2)] and ZnTTP was carried out in the ratio as given in example I. The resulting conductivity was 10−8 S/cm.
In a manner analogous to Example I, mixed vapour deposition of bis-[1,3-dimethyl-2-ethyl-1,2-dihydrobenzimidazolyl-(2)] and ZnPc was carried out in the ratio as given in example I. The resulting conductivity was 10−4 S/cm.
In a manner analogous to Example I, mixed vapour deposition of bis-[1,3-dimethyl-2-N-pyrrolidyl-1,2-dihydrobenzimidazolyl-(2)] and ZnTPP was carried out in the ratio as given in example I. The resulting conductivity was 10−4 S/cm.
In a manner analogous to Example I, mixed vapour deposition of bis-[1,3,5,6-tetramethyl-2-isopropyl-1,2-dihydrobenzimidazolyl-(2)] and zinc octaethylporphyrin ZnOEP was carried out in the ratio as given in example I. The resulting conductivity was 5×10−8 S/cm.
In a manner analogous to Example I, mixed vapour deposition of 2-isopropyl-1,3-dimethyl-2,3,6,7-tetrahydro-1H-5,8-dioxa-1,3-diazacyclopenta[b]naphthene and ZnTPP was carried out in the ratio as given in example I. The resulting conductivity was 1.8×10−4 S/cm.
In a manner analogous to Example I, mixed vapour deposition of 2-isopropyl-1,3-dimethyl-2,3,6,7-tetrahydro-1H-5,8-dioxa-1,3-diazacyclopenta[b]naphthene and ZnOEP was carried out in the ratio as given in example I. The resulting conductivity was 5×10−8 S/cm.
In a manner analogous to Example I, mixed vapour deposition of 2-isopropyl-1,3-dimethyl-2,3,6,7-tetrahydro-1H-5,8-dioxa-1,3-diazacyclopenta[b]naphthene and ZnPc was carried out in the ratio as given in example I. The resulting conductivity was 2.2×10−8 S/cm.
In a manner analogous to Example I, mixed vapour deposition of bis-[1,3-dimethyl-2-isopropyl-1,2-dihydroimidazolyl-(2)] and ZnPc was carried out in the ratio as given in example I. The resulting conductivity was 10−3 S/cm.
In a manner analogous to Example I, mixed vapour deposition of bis-[1,3-diethyl-2-methyl-1,2-dihydrobenzthiazolyl-(2)] and ZnPc was carried out in the ratio as given in example I. The resulting conductivity was 3.8×10−7 S/cm.
The features of the invention which are disclosed in the above description and in the claims may be essential both individually and in an combination with one another for an implementation of the invention in its various embodiments.
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US4960916 29 Sep 1989 2 Oct 1990 United States Of America As Represented By The Secretary Of The Navy Organometallic antimony compounds useful in chemical vapor deposition processes
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Clasificación internacional C07D235/02, C08G61/00, H01L51/00, H01L51/30
Clasificación cooperativa C07D235/02, H01L51/002, H01L51/0071, H01L51/0081, H01L51/0051, C08G61/00, H01L51/0067, Y02E10/549