Method for producing an organic electronic component, and organic electronic component

Abstract

A metal complex is disclosed. In an embodiment a metal complex includes at least one metal atom M and at least one ligand L attached to the metal atom M, wherein the ligand L has the following structure: ##STR00001## wherein E.sup.1 and E.sup.2 are oxygen, wherein the substituent R.sup.1 is selected from the group consisting of branched or unbranched, fluorinated aliphatic hydrocarbons with 1 to 10 C atoms, wherein n=1 to 5, wherein the substituent R.sup.2 is selected from the group consisting of branched or unbranched aliphatic hydrocarbons with 1 to 10 C atoms, aryl and heteroaryl, wherein m>0 to at most 5−n, and wherein the metal M is a main group metal of groups 13 to 15 of the periodic table of elements.

Claims

1. A metal complex comprising: at least one metal atom M and at least one ligand L attached to the at least one metal atom M, wherein the at least one ligand L has the following structure: ##STR00014## wherein E.sup.1 and E.sup.2 are oxygen, wherein the substituent R.sup.1 is selected from branched or unbranched, fluorinated aliphatic hydrocarbons with 1 to 10 C atoms, wherein n=1 to 5, wherein the substituent R.sup.2 is selected from branched or unbranched aliphatic hydrocarbons with 1 to 10 C atoms, aryl and heteroaryl, wherein m>0 to at most 5−n, and wherein the at least one metal atom M is a main group metal of groups 13 to 15 of the periodic table of elements.

2. The metal complex according to claim 1, wherein the at least one metal atom M is Bi.

3. The metal complex according to claim 1, wherein the at least one metal atom M is Bi in an oxidation state III.

4. The metal complex according to claim 1, wherein the substituent R.sup.1 is an at least difluorinated substituent.

5. The metal complex according to claim 1, wherein the substituent R.sup.1 is a perfluorinated substituent.

6. The metal complex according to claim 1, wherein the substituent R.sup.1 is a —CF.sub.3 group.

7. The metal complex according to claim 1, wherein the substituent R.sup.1 is a —CF.sub.3 group and the at least one metal atom M is Bi.

8. The metal complex according to claim 1, wherein the at least one ligand L is attached to the at least one metal atom M by the following form of coordination: ##STR00015##

9. The metal complex according to claim 1, wherein the at least one ligand L is ##STR00016##

10. The metal complex according to claim 1, wherein the at least one metal atom M is Bi and the at least one ligand L is ##STR00017##

11. The metal complex according to claim 1, wherein the at least one ligand L is selected from the group consisting of: ##STR00018##

12. The metal complex according to claim 1, wherein the at least one metal atom M is Bi and the at least one ligand L is selected from the group consisting of: ##STR00019##

13. A metal complex comprising: at least one metal atom M and at least one ligand L attached to the at least one metal atom M, wherein the at least one ligand L has the following structure: ##STR00020## wherein E.sup.1 and E.sup.2 are oxygen, wherein the substituent R.sup.1 is selected from branched or unbranched, fluorinated aliphatic hydrocarbons with 1 to 10 C atoms, wherein n=1 to 5, wherein the substituent R.sup.2 is selected from the group consisting of —CN, branched or unbranched aliphatic hydrocarbons with 1 to 10 C atoms, aryl and heteroaryl, and wherein m=0 to at most 5−n.

14. The metal complex according to claim 13, wherein the at least one metal atom M is a main group metal of groups 13 to 15 of the periodic table of elements.

15. The metal complex according to claim 14, wherein the at least one metal atom M is Bi in an oxidation state III.

16. The metal complex according to claim 13, wherein the at least one ligand L is attached to the at least one metal atom M by the following form of coordination: ##STR00021##

17. The metal complex according to claim 13, wherein the at least one ligand L is selected from the group consisting of: ##STR00022##

18. The metal complex according to claim 13, wherein the at least one metal atom M is Bi and the at least one ligand L is selected from the group consisting of: ##STR00023##

19. The metal complex according to claim 13, wherein the ligand L is selected from the group consisting of: ##STR00024##

20. The metal complex according to claim 13, wherein the at least one metal atom M is Bi and the at least one ligand L is selected from the group consisting of: ##STR00025##

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Further details, features and advantages of the subject matter of the invention may be inferred from the following description of the figures and the associated examples and reference examples.

(2) In the figures:

(3) FIG. 1 is a schematic diagram of the structure of an organic light-emitting diode;

(4) FIG. 2 is a schematic diagram of the structure of an organic solar cell;

(5) FIG. 3 is a schematic diagram of a possible cross-section of an organic field-effect transistor;

(6) FIG. 4 shows the structure of a prior art point source;

(7) FIG. 5 shows the structure of a linear source, taking a schematic diagram of a linear source;

(8) FIG. 6 shows, with regard to example I, current density plotted against voltage for the undoped matrix material and for the doped matrix material;

(9) FIG. 7 shows, with regard to example II, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris-3,5-trifluoromethylbenzoate;

(10) FIG. 8 shows, with regard to example II, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris-3,5-trifluoromethylbenzoate;

(11) FIG. 9 shows, with regard to reference example I, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(2,6-difluorobenzoate) for the doped matrix material obtained by deposition by means of point sources;

(12) FIG. 10 shows, with regard to reference example I, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(2,6-difluorobenzoate);

(13) FIG. 11 shows, with regard to reference example II, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(4-fluorobenzoate) for the doped matrix material obtained by deposition by means of point sources;

(14) FIG. 12 shows, with regard to reference example II, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(4-fluorobenzoate);

(15) FIG. 13 shows, with regard to reference example III, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(3-fluorobenzoate) for the doped matrix material obtained by deposition by means of point sources;

(16) FIG. 14 shows, with regard to reference example III, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(3-fluorobenzoate);

(17) FIG. 15 shows, with regard to reference example IV, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(3,5-difluorobenzoate) for the doped matrix material obtained by deposition by means of point sources;

(18) FIG. 16 shows, with regard to reference example IV, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(3,5-difluorobenzoate);

(19) FIG. 17 shows, with regard to reference example V, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(3,4,5-trifluorobenzoate) for the doped matrix material obtained by deposition by means of point sources;

(20) FIG. 18 shows, with regard to reference example V, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(3,4,5-trifluorobenzoate);

(21) FIG. 19 shows, with regard to reference example VI, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(perfluorobenzoate) for the doped matrix material obtained by deposition by means of point sources;

(22) FIG. 20 shows, with regard to reference example VI, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(perfluorobenzoate);

(23) FIG. 21 shows, with regard to reference example VII, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(4-perfluorotoluate) for the doped matrix material obtained by deposition by means of point sources;

(24) FIG. 22 shows, with regard to reference example VII, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(4-perfluorotoluate);

(25) FIG. 23 shows, with regard to reference example VIII, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(trifluoroacetate) for the doped matrix material obtained by deposition by means of point sources;

(26) FIG. 24 shows, with regard to reference example VIII, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(trifluoroacetate);

(27) FIG. 25 shows, with regard to reference example IX, current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(triacetate) for the doped matrix material obtained by deposition by means of point sources; and

(28) FIG. 26 shows, with regard to reference example IX, current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(triacetate).

DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

(29) FIG. 1 is a schematic diagram of the structure of an organic light-emitting diode (10). The light-emitting diode is made up of a glass layer (1); Transparent Conductive Oxide (TCO) or PEDOT:PPS or PANI layer (2); hole-injection layer (3); hole-transport layer (HTL) (4); emitter layer (EML) (5); hole-blocking layer (HBL) (6); electron-transport layer (ETL) (7); electron-injection layer (8) and a cathode layer (9);

(30) FIG. 2 is a schematic diagram of the structure of an organic solar cell with PIN structure (20) which converts light (21) into electrical current. The solar cell consists of a layer of indium-tin oxide (22); a p-doped layer (23); an absorption layer (24); an n-doped layer (25) and a metal layer (26);

(31) FIG. 3 is a schematic diagram of a possible cross-section of an organic field-effect transistor (30). A gate electrode (32), a gate dielectric (33), a source and drain contact (34+35) and an organic semiconductor (36) are applied onto a substrate (31). The crosshatched portions indicate the portions where contact doping is helpful.

(32) FIG. 4 shows the structure of a prior art point source from Creaphys. The point source has a crucible (41). The material to be deposited is evaporated in the crucible under vacuum conditions. Once the material has evaporated, the molecules leave the point source via the outlet orifice (42). Because of the large average free path length under a vacuum (10.sup.−5 to 10.sup.−6 mbar), the molecules, for example, of a metal complex acting as dopant, land without further collisions on the substrate. This means that a material needs to be thermally stable only slightly above the sublimation temperature for it to be possible to deposit it undecomposed on the substrate. In particular, a doping agent deposited by means of a point source does not land on walls of the source, but, by being directly arranged at the orifice of the source, may instead be deposited directly on the substrate to be coated. The region of the crucible, in which the dopant evaporates, together with the outlet orifice and the substrate are thus in a rectilinear arrangement. In particular, the dopant can be deposited without being deflected via line systems or spraying systems before it lands on the substrate.

(33) FIG. 5 shows the structure of a linear source, taking a schematic diagram of a linear source from Vecco by way of example. The linear source has a crucible (51), which may be removable. Once the material to be deposited, for example, the dopant, has evaporated in the crucible, the dopant, which is in the gas phase, is guided via lines (53) to the outlet orifice (52). The outlet orifice (52) may here, for example, take the form of a slot or consist of a row of holes. The linear source does not provide the dopant with direct, rectilinear access to the substrate, the dopant instead being often repeatedly deflected in the linear source. The dopant consequently collides numerous times with the walls of the linear source. The linear source may furthermore contain controllable valves (54), flow controllers (56) and corresponding cabling (55) for electronic control for instance of the heating device or the valves. Purposeful guidance of the gas stream means that large-area deposition can be achieved particularly effectively.

(34) FIG. 6 shows, for example, I current density plotted against voltage for the undoped matrix material and for the doped matrix material. The matrix material used was the hole conductor 2,2′,7,7′-tetra(N,N-ditolyl)amino-9,9-spiro-bifluorene, abbreviated to spiro-TTB. The current density-voltage characteristic curve demonstrates the adequate doping behavior of 15% Cu(3,5-tfmb) in the hole conductor spiro-TTB.

(35) FIG. 7 shows with regard to example II current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris-3,5-trifluoromethylbenzoate. The measurements were made on doped matrix materials produced by means of point sources in order to permit a comparison of electrical properties under identical conditions with the comparative examples. Measurement was made at each of three different doping agent contents. The voltage characteristic curve demonstrates good conductivities and substantiates the good doping agent strength of bismuth(III) tris-3,5-trifluoromethylbenzoate.

(36) FIG. 8 shows with regard to example II current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris-3,5-trifluoromethylbenzoate.

(37) FIG. 9 shows with regard to reference example I current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(2,6-difluorobenzoate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(38) FIG. 10 shows with regard to reference example I current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(2,6-difluorobenzoate).

(39) FIG. 11 shows with regard to reference example II current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(4-fluorobenzoate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(40) FIG. 12 shows with regard to reference example II current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(4-fluorobenzoate).

(41) FIG. 13 shows with regard to reference example III current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(3-fluorobenzoate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(42) FIG. 14 shows with regard to reference example III current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(3-fluorobenzoate).

(43) FIG. 15 shows with regard to reference example IV current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(3,5-difluorobenzoate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(44) FIG. 16 shows with regard to reference example IV current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(3,5-difluorobenzoate).

(45) FIG. 17 shows with regard to reference example V current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(3,4,5-trifluorobenzoate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(46) FIG. 18 shows with regard to reference example V current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(3,4,5-trifluorobenzoate).

(47) FIG. 19 shows with regard to reference example VI current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(perfluorobenzoate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(48) FIG. 20 shows with regard to reference example VI current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(perfluorobenzoate).

(49) FIG. 21 shows with regard to reference example VII current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(4-perfluorotoluate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(50) FIG. 22 shows with regard to reference example VII current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(4-perfluorotoluate).

(51) FIG. 23 shows with regard to reference example VIII current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(trifluoroacetate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(52) FIG. 24 shows with regard to reference example VIII current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(trifluoroacetate).

(53) FIG. 25 shows with regard to reference example IX current density plotted against voltage and current density plotted against external field strength for 1-TNata doped with bismuth(III) tris(triacetate) for the doped matrix material obtained by deposition by means of point sources. Measurement was made at each of three different doping agent contents.

(54) FIG. 26 shows with regard to reference example IX current density plotted against voltage and current density plotted against external field strength for the matrix materials 1-TNata, spiro-TTB and α-NPB doped with bismuth(III) tris(triacetate).

(55) The two examples I and II will be presented below. The two metal complexes copper(I) bis-trifluoromethylbenzoate (example I) and bismuth(III) tris-3,5-trifluoromethylbenzoate (example II) are extraordinarily thermally stable with decomposition temperatures distinctly above the sublimation temperature thereof. Both complexes can be deposited by means of sources in which the complexes undergo collisions with at least one wall of the source. For example, both complexes have stability which is sufficiently high for gas-phase deposition via linear sources. This has been confirmed experimentally by “ampoule tests”.

(56) None of the further reference examples, namely reference examples I to IX, exhibited sufficient stability in ampoule tests. The inventors have established experimentally that these substances are not suitable for deposition by means of sources in which the complexes undergo collisions.

(57) The electrical properties of the respective doped layers are likewise investigated below. Since each of the metal complexes of reference examples I to IX is not sufficiently stable for deposition by means of sources in which collisions occur with at least one wall of the source, measurements were made on organic electrical layers deposited via point sources and compared with one another. The complexes of reference examples I to IX, for example, are not sufficiently stable for deposition by means of linear sources.

Example I

(58) Example I relates to the metal complex copper(I) bistrifluoromethylbenzoate, hereinafter abbreviated to Cu(3,5-tfmb).

(59) In general, many copper(I) complexes of fluorinated benzoate derivatives may be produced in the following manner:

(60) ##STR00012##

(61) A multiplicity of the metal complexes used in the method according to the invention may be produced in similar manner.

(62) The metal complex 3,5-bis-(trifluoromethylbenzoate) may for instance accordingly be obtained from Cu(I) trifluoroacetate in accordance with the following method:

(63) 5 g (7.08 mmol) Cu(I) trifluoroacetate is weighed out together with 7.5 g (29.03 mmol) 3,5-bis-(trifluoromethylbenzoic acid) in a 250 ml two-necked flask under inert gas (for example, in a glove box). The mixture is combined with 80 ml toluene and 70 ml benzene, giving rise to a greenish reaction solution. The latter is gently refluxed overnight (bath temperature approx. 90° C.), whereupon the solvent is removed by distillation. A grayish cream-colored product remains, which is dried under a vacuum. Yield is 6.98 g (76%) after single sublimation. The sublimation range of the substance is 160-180° C. at 2×10.sup.−5 mbar.

(64) It was possible to demonstrate by ampoule tests that Cu(3,5-tfmb) is stable up to at least 225° C.

(65) In ampoule tests, approx. 100 to 500 mg of the substance to be investigated is melted at a base pressure of 10.sup.−5 to 10.sup.−6 mbar. The ampoule is then heated in an oven and kept at the respective temperature for approx. 100 hours. It is possible to recognize by visual inspection whether the metal complex has decomposed because decomposition leads to discoloration, frequently to a brown color. Finally, after around 100 hours at the first test temperature, the ampoule is further heated in 10-20 Kelvin steps and again left in the oven at the new test temperature for around 100 hours. The experiment is continued until it is finally possible to conclude that decomposition has occurred due to discoloration.

(66) In addition, in a control experiment, in each case following the visual determination, a further ampoule containing a new sample of the same metal complex to be tested is again heated in the oven for around 100 hours. Heating here proceeds to a temperature just below the visually determined decomposition temperature. The sample treated in this manner is then investigated by elemental analysis and in this manner the stability of the complex is confirmed on the basis of the elemental composition.

(67) For copper(I) bis-trifluoromethylbenzoate according to example I, ampoule tests were carried out for three different temperatures: 210° C., 230° C. and 240° C.

(68) The measurements demonstrate that the complex is stable up to at least 225° C. This was confirmed by means of elemental analysis.

(69) Cu(3,5-tfmb) is thus suitable for deposition from the gas phase also by means of sources in which the complex collides with at least one of the walls of the sources. Deposition from the gas phase via linear sources is possible, for example.

(70) Layers doped with Cu(3,5-tfmb) have very good optical transparency in the visible range. Cu(3,5-tfmb) is additionally distinguished by sufficiently good doping agent strength.

(71) As is furthermore shown by FIG. 6, organic layers doped with Cu(3,5-tfmb) have good conductivities.

Example II

(72) Example II relates to a method according to the invention, wherein the metal complex is bismuth(III) tris-3,5-trifluoromethylbenzoate, hereinafter abbreviated to Bi(3,5-tfmb).sub.3.

(73) Bismuth complexes according to example II and the metal complexes described below of reference examples I to VII were produced in accordance with the following general method according to scheme 1:

(74) ##STR00013##

(75) For Bi(3,5-tfmb).sub.3, residues R.sup.B and R.sup.D, thus the residues in 3,5-position, are each CF.sub.3 substituents and residues R.sup.A, R.sup.C and R.sup.E are each hydrogen atoms.

(76) After purification by means of sublimation, it was confirmed by elemental analysis that Bi(3,5-tfmb).sub.3 had been obtained (measured: carbon in %33.5; hydrogen in %0.5; calculated: carbon in %33.06; hydrogen in %0.92).

(77) The thermal stability of bismuth(III) tris-3,5-trifluoromethylbenzoate was determined with the assistance of ampoule tests, as have already been described in connection with example I. According to said tests, the metal complex is stable at 330° C. even in the event of thermal treatment over an interval of time of 144 hours. No discoloration in the ampoule is to be observed at temperatures of below 330° C. Only from 330° C. does slight discoloration become visible. Elemental analysis data also confirm that, within the limits of statistical error, the complex is thermally stable up to 330° C.

(78) As shown in table 1, similar tests were carried out in each case for 144 hours at the temperatures 260° C., 280° C., 315° C. and 330° C. Samples of the heat-treated substance were in each case investigated by means of elemental analysis, with the carbon content being determined. On the basis of the deviation of the carbon content determined in this manner from the expected carbon content of the undecomposed complex, it is possible to draw conclusions as to the degree of decomposition of the complex after the respective heat treatment. The inventors were able to demonstrate on the basis of the test series that bismuth(III) tris-3,5-trifluoromethylbenzoate according to example II has particularly high thermal stability and, taking account of statistical error, only exhibits clear signs of decomposition at temperatures of above 330° C.

(79) Table 1: Determination of carbon content by means of elemental analysis at two different locations (location A and location B) of the ampoule on which substance has in each case been deposited after the ampoule test.

(80) The slight deviations of the determined carbon content up to temperatures of 330° C. from the theoretically calculated content (of 33.06%) demonstrate the high thermal stability of bismuth(III) tris-3,5-trifluoromethylbenzoate. Clear signs of decomposition of the complex are only observed at temperatures of above 330° C.

(81) TABLE-US-00001 TABLE 1 Determination of carbon content by means of elemental analysis at two different locations (location A and location B) of the ampoule on which substance has in each case been deposited after the ampoule test. The slight deviations of the determined carbon content up to temperatures of 330° C. from the theoretically calculated content (of 33.06%) demonstrate the high thermal stability of bismuth(III) tris-3,5-trifluoromethylbenzoate. Clear signs of decomposition of the complex are only observed at temperatures of above 330° C. Location A Location B 3× sublimated no material theoret. value + 0.44% C. material 144 h at 260° C. theoret. value + 0.49% C. theoret. value + 0.05% C. 144 h at 280° C. theoret. value + 0.63% C. theoret. value + 0.12% C. 144 h at 300° C. theoret. value + 0.49% C. no material 144 h at 315° C. theoret. value + 0.47% C. theoret. value + 0.18% C. 144 h at 330° C. theoret. value + 0.14% C. decomposition

(82) Elemental analysis thus confirms stability of the complex up to 330° C. taking account of statistical error.

(83) Doping agents with fluorinated alkyl substituents R.sup.1, as is apparent from the example of bismuth(III) tris-3,5-trifluoromethylbenzoate, are particularly suitable, thanks to their high thermal stability, for gas-phase deposition by means of sources in which the metal complexes, i.e., the dopants, undergo collisions with at least one wall of the source. For example, the metal complexes are sufficiently stable to be depositable from the gas phase via linear sources without decomposition.

(84) Layers doped with Bi(3,5-tfmb).sub.3 layers have very good optical transparency in the visible range.

(85) Bi(3,5-tfmb).sub.3 is additionally distinguished by sufficiently good doping agent strength. This is further clarified by the experimental data summarized below.

(86) FIGS. 7 and 8 and tables 2 and 3 summarize the electrical properties of organic layers doped with Bi(3,5-tfmb).sub.3.

(87) Table 2: Summary of the electrical properties of i-TNata doped with Bi(3,5-tfmb).sub.3. Electrical properties are in particular investigated on the matrix at three different doping agent contents (1:8,1:4 and 1:2).

(88) TABLE-US-00002 TABLE 2 Summary of the electrical properties of matrix materials 1-TNata, with Bi(3,5-tfmb).sub.3.Math. Electrical properties are in particular investigated on the matrix at three different doping agent contents (1:8, 1:4, 1:2). (1:8) (1:4) (1:2) Exp. molar ratio 1/8.08 (7.64 vol. %.) 1/4.07 (14.11 vol. %) 1/1.99 (25.14 vol. %) σ.sub.0 (S .Math. cm.sup.−1) 4.08 .Math. 10.sup.−7 (±1.00%) 7.01 .Math. 10.sup.−7 (±4.61%) 5.27 .Math. 10.sup.−7 (±0.88%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 1.96 .Math. 10.sup.7 (±5.65%) 1.72 .Math. 10.sup.−6 (±5.14%) 4.64 .Math. 10.sup.5 (±3.86%) E.sub.bi (kV .Math. cm ) <0.25 ε.sub.r Too conductive r + 1 3.24 (±1.72%) 2.33 (± 4.61%) 1.59 (±2.42%) μ.sub.0 (cm.sup.2 .Math. V.sup.−1 .Math. s.sup.−1) 3.20 .Math. 10.sup.−5 (±25%)* Ballistic γ (cm.sup.1/2 .Math. V.sup.1/2) 2.54 .Math. 10.sup.−4 (±4.9%)*

(89) The electrical properties for the various materials shown in table 2 and all the further tables were determined by measurements made on 200 nm thick organic layers supported on ITO (indium tin oxide) substrates and obtained by coevaporation via point sources.

(90) “Exp. molar ratio” here in each case denotes the molar ratio of matrix material and the metal complex. “σ.sub.0” denotes the conductivity of the measured organic electronic layer. “ρ.sub.c.;0” denotes the contact resistance. “E.sub.bi” denotes the electrical field strength of the internal electrical field of the semiconductor material (“built-in electric field”; this field strength is obtained from the difference in the work function between anode and cathode of the organic electronic component). “ε.sub.r” indicates the dielectric constant of the material obtained by coevaporation.

(91) A series of further parameters was determined in connection with the transport regime of the charge carriers in the organic electrical layer, as are described in various theories of conductivity in the literature. “r” here denotes an empirical factor (“trap distribution factor”) which describes an exponential distribution in accordance with the charge carrier transport models (Steiger et al. “Energetic trap distributions in organic semiconductors” Synthetic Metals 2002, 129 (1), 1-7; Schwoerer et al. “Organic Molecular Solids”, Wiley-VCH, 2007). “μ.sub.0” denotes charge carrier mobility and γ denotes the field-activation factor. γ is for instance of significance in connection with a description of charge transport according to the Murgatroyd equation: Murgatroyd, P. N. “Theory of space-charge-limited current enhanced by Frenkel effect” Journal of Physics D: Applied Physics 1979, 3 (2), 151.

(92) The terms “too conductive”, “ballistic”, “no ohmic contact”, “trapping”, “aging”, “no TFLC”, “compliance” used in tables 2 to 31 in each case have the following meanings: “Too conductive” means that the measurement is not meaningful due to excessively high layer conductivity. “No ohmic contact” indicates that no electrical contact was present. “Compliance” indicates that the preset current limitation of the measuring instrument was achieved. “TFLC” denotes “trap-filled limited regime” in accordance with the stated papers by Steiger et al. and Schwoerer et al. and refers to a transport regime for the charge carriers of the organic electrical layer. The terms “ballistic”, “trapping” and “aging” here refer to further transport regimes in accordance with the various models of conductivity described in the literature. The various conductivity regimes may here be recognized from the exponent of current-voltage dependency.

(93) The respective abbreviations also apply similarly for tables 3 to 21.

(94) Table 3: Summary of the electrical properties of matrix materials i-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(3,5-tfmb).sub.3. The electrical properties when doping different matrix materials are compared.

(95) TABLE-US-00003 TABLE 3 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(2,6-dfb).sub.3.Math. The electrical properties when doping different matrix materials are compared. I-TNata α-NPB spiro-TTB Exp. molar ratio 1/1.99 (25.14 vol. %) 11.99 (35.32 vol. %) 1/2.00 (19.99 vol. %) σ.sub.0 (S .Math. cm.sup.−1) 5.27 .Math. 10.sup.−7 (±0.88 %) 1.05 .Math. 10.sup.−7 (±1.23%) 4.60 .Math. 10.sup.−6 (±0.63%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 4.64 .Math. 10.sup.5 (±3.86%) 3.55 .Math. 10.sup.8 (±7.18%) 4.76 .Math. 10.sup.5 (±4.76%) E.sub.bi (kV .Math. cm ) <0.25 ε.sub.r Too conductive 2.15 (±5.07%) Too conductive r + 1 1.59 (± 2.42%) 3.15 (±3.71%) 2.24 (±3.01 %) μ.sub.0 (cm.sup.2 .Math. V.sup.−1 .Math. s.sup.−1) Ballistic 5.28 .Math. 10.sup.−5 (±37.3%) Ballistic γ (cm.sup.1/2 .Math. V.sup.1/2) 1.88 .Math. 10.sup.−6 (±11.4%)

(96) The measurements confirm that matrix materials doped with Bi(3,5-tfmb).sub.3 have good electrical properties, in particular sufficiently good conductivities.

(97) This is clarified below by a comparison with the electrical properties of a multiplicity of further complexes which, in contrast with Cu(3,5-tfmb) according to example I and Bi(3,5-tfmb).sub.3 according to example II, did not exhibit sufficient thermal stability in ampoule tests and are therefore not suitable for deposition from the gas phase by means of sources in which collisions occur with at least one wall of the source.

Reference Example I

(98) Reference example I relates to the use of bismuth(III) tris(2,6-difluorobenzoate), abbreviated to Bi(2,6-dfb).sub.3, as a metal complex for gas-phase deposition.

(99) Bi(2,6-dfb).sub.3 was synthesized in accordance with scheme 1. For Bi(2,6-dfb).sub.3, residues R.sup.A and R.sup.E in scheme 1 are in each case fluorine atoms and the remaining substituents R.sup.B, R.sup.C and R.sup.D in each case hydrogen atoms.

(100) After purification by means of sublimation, it was confirmed by elemental analysis that Bi(2,6-tfmb).sub.3 had been obtained (measured: carbon in %36.2; hydrogen in %1.5; calculated: carbon in %37.06; hydrogen in %1.32).

(101) FIGS. 9 and 10 and tables 4 and 5 summarize the electrical properties of organic layers doped with Bi(2,6-dfb).sub.3.

(102) Table 4: Summary of the electrical properties of i-TNata doped with Bi(2,6-dfb).sub.3.

(103) TABLE-US-00004 TABLE 4 Summary of the electrical properties of 1-TNata, with Bi(2,6-dfb).sub.3.Math. (1:8) (1:4) (1:2) Exp. molar ratio 1/8.07 (4.57 vol. %) 13.96 (8.90 vol. %) 1/2.00 (16.22 vol. %) σ.sub.0 (S .Math. cm.sup.−1) 6.98 .Math. 10.sup.−8 (±2.18%) 3.62 .Math. 10.sup.−8 (±2.56%) 4.80 .Math. 10.sup.−8 (±1.25 %) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) no ohmic contact E.sub.bi (kV .Math. cm.sup.−1) 13.6 (±19.3%) 12.3 (±12.2%) 9.50 (±13.2%) ε.sub.r 2.48 (±4.21%) 2.45 (±11.9%) 3.51 (±53.2%) r + 1 15.2 (±6.60%) 13.3 (±6.80%) 12.1 (±6.11%) μ.sub.0 (cm.sup.2 .Math. V.sup.−1 .Math. s.sup.−1) 4.82 .Math. 10.sup.−6 (±8.71%) 3.18 .Math. 10.sup.−6 (±16.6%) 3.95 .Math. 10.sup.−6 (±58.2%) γ (cm.sup.1/2 .Math. V.sup.1/2) 2.01 .Math. 10.sup.−3 (±0.81%) 1.78 .Math. 10.sup.−3 (±0.89%) 9.82 .Math. 10.sup.−4 (±1.23%)

(104) Table 5: Summary of the electrical properties of matrix materials i-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(2,6-dfb).sub.3.

(105) TABLE-US-00005 TABLE 5 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(2,6-dfb).sub.3.Math. I-TNata α-NPB spiro-TTB Exp. molar ratio 1/2.00 (16.22 vol. %) 1/2.02 (23.72 vol. %) 1/1.96 (12.87 vol. %) σ.sub.0 (S .Math. cm.sup.−1) 4.80 .Math. 10.sup.−8 (±1.25 %) 4.89 .Math. 10.sup.−9 (±2.82 %) 2.04 .Math. 10.sup.−7 (±1.90%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) no ohmic contact E.sub.bi (kV .Math. cm.sup.−1) 9.50 (±13.2%) 30.0 (±9.17%) 12.5 (±46.0%) ε.sub.r 3.51 (±53.2%) 2.34 (±3.83%) 3.01 (±5.83%) r + 1 12.1 (±6.11%) 22.5 (±54.9%) 17.0 (±4.08%) μ.sub.0 (cm.sup.2 .Math. V.sup.−1 .Math. s.sup.−1) 3.95 .Math. 10.sup.−6 (±58.2 %) 7.09 .Math. 10.sup.−7 (±8.73%) 1.45 .Math. 10.sup.−5 (±9.65%) γ (cm.sup.1/2 .Math. V.sup.1/2) 9.82 .Math. 10.sup.−4 (±1.23%) 4.94 .Math. 10.sup.−3 (±1.27%) 4.33 .Math. 10.sup.−3 (±0.78%)

Reference Example II

(106) Reference example II relates to the use of bismuth (III) tris(4-fluorobenzoate), abbreviated to Bi(4-fb).sub.3, as a metal complex for gas-phase deposition.

(107) Bi(4-fb).sub.3 was synthesized in accordance with scheme 1. For Bi(4-fb).sub.3, the residues R.sup.A, R.sup.B, R.sup.D and R.sup.E in scheme 1 are hydrogen atoms and only R.sup.C is a fluorine atom.

(108) After purification by means of sublimation, it was confirmed by elemental analysis that Bi(4-fb).sub.3 had been obtained (measured: carbon in %42.4; hydrogen in %2.3; calculated: carbon in %40.26; hydrogen in %1.92).

(109) FIGS. 11 and 12 and tables 6 and 7 summarize the electrical properties of organic layers doped with Bi(4-fb).sub.3.

(110) Table 6: Summary of the electrical properties of i-TNata doped with Bi(4-fb).sub.3.

(111) TABLE-US-00006 TABLE 6 Summary of the electrical properties of 1-TNata, with Bi(4-fb).sub.3.Math. (1:8) (1:4) (1:2) Exp. molar ratio 18.09 (4.54 vol. %) 1/4.02 (8.74 vol. %) 1/1.99 (16.20 vol. %) σ.sub.0 (S .Math. cm.sup.−1) 2.33 .Math. 10.sup.−7 (±1.60%) 1.62 .Math. 10.sup.−7 (±1.80%) 2.50 .Math. 10.sup.−7 (±1.21%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) no ohmic contact 3.80 .Math. 10.sup.8 (±9.84%) E.sub.bi (kV .Math. cm.sup.−1) 6.38 (±64.7%) 3.13 (±100%) <0.25 ε.sub.r 2.75 (±2.63%) 2.52 (±16.4%) 2.91 (±9.61%) r + 1 18.5 (±8.97%) 9.02 (±2.62%) 5.40 (±2.05%) μ.sub.0 (cm.sup.2 .Math. V.sup.−1 .Math. s.sup.−1) 3.74 .Math. 10.sup.−5 (±7.51%) 1.19 .Math. 10.sup.−5 (±21.5%) 3.30 .Math. 10.sup.−5 (±15.4%) γ (cm.sup.1/2 .Math. V.sup.1/2) 2.45 .Math. 10.sup.−3 (±1.15%) 1.59 .Math. 10.sup.−3 (±0.93%) 1.12 .Math. 10.sup.−4 (±6.68%)

(112) Table 7: Summary of the electrical properties of matrix materials i-TNata, α-NPB and spiro-TTB doped with

(113) (1:2) Bi(4-fb).sub.3.

(114) TABLE-US-00007 TABLE 7 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(4-fb).sub.3. 1-TNata α-NPB spiro-TTB Exp. molar ratio 1/1.99 (16.20 .sub.vol. %) 1/2.01 (23.74 .sub.vol. %) 1/1.97 (12.74 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 2.50 .Math. 10.sup.−7 (±1.21%) 5.72 .Math. 10.sup.−7 (±1.11%) 1.99 .Math. 10.sup.−6 (±0.81%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 3.80 .Math. 10.sup.−8 (±9.84%) no ohmic contact E.sub.bi (kV .Math. cm.sup.−1) <0.25 7.75 (±80.7%) ε.sub.r 291 (±9.61%) 2.36 (±7.06%) 3.32 (±7.14%) r + 1 5.40 (±2.05%) 7.23 (±17.06%) 13.7 (±2.08%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) 3.30 .Math. 10.sup.−5 (±15.4%) Trapping Aging γ (cm.sup.1/2 .Math. V.sup.1/2) 1.12 .Math. 10.sup.−4 (±6.68%)

Reference Example III

(115) Reference example III relates to the use of bismuth(III) tris(3-fluorobenzoate), abbreviated to Bi(3-fb).sub.3, as a metal complex for gas-phase deposition.

(116) Bi(3-fb).sub.3 was synthesized in accordance with scheme 1. For Bi(3-fb).sub.3, the residues R.sup.A, R.sup.C, R.sup.D and R.sup.E in scheme 1 are hydrogen atoms and only R.sup.B is a fluorine atom.

(117) After purification by means of sublimation, it was confirmed by elemental analysis that Bi(3-fb).sub.3 had been obtained (measured: carbon in %39.2; hydrogen in %2.3; calculated: carbon in %40.26; hydrogen in %1.92).

(118) FIGS. 13 and 14 and tables 8 and 9 summarize the electrical properties of organic layers doped with Bi(3-fb).sub.3.

(119) Table 8: Summary of the electrical properties of i-TNata doped with Bi(3-fb).sub.3.

(120) TABLE-US-00008 TABLE 8 Summary of the electrical properties of 1-TNata doped with Bi(3-fb).sub.3. (1:8) (1:4) (1:2) Exp. molar ratio 1/8.16 (4.62 .sub.vol. %) 1/3.97 (9.07 .sub.vol. %) 1/1.94 (16.92 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 1.73 .Math. 10.sup.−7 (±1.51%) 1.48 .Math. 10.sup.−7 (±0.96%) 1.38 .Math. 10.sup.−7 (±1.27%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) no ohmic contact 9.07 .Math. 10.sup.8 (±9.56%) E.sub.bi (kV .Math. cm.sup.−1) 8.38 (±25.4%) 0.63 (±100%) <0.25 ε.sub.r 3.57 (±35.5%) 3.22 (±9.91%) 3.64 (±6.24%) r + 1 12.5 (±3.23%) 6.22 (±1.90%) 4.67 (±2.12%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) 9.07 .Math. 10.sup.−6 (±40.2%) 7.52 .Math. 10.sup.−6 (±14.8%) 3.37 .Math. 10.sup.−6 (±11.6%) γ (cm.sup.1/2 .Math. V.sup.1/2) 1.52 .Math. 10.sup.−3 (±1.04%) 1.36 .Math. 10.sup.−3 (±1.19%) 1.95 .Math. 10.sup.−3 (±1.13%)

(121) Table 9: Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with

(122) (1:2) Bi(3-fb).sub.3.

(123) TABLE-US-00009 TABLE 9 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(3-fb).sub.3. 1-TNata α-NPB spiro-TTB Exp. molar ratio 1/1.94 (16.92 .sub.vol. %) 1/2.05 (23.85 .sub.vol. %) 1/2.00 (12.86 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 1.38 .Math. 10.sup.−7 (±1.27%) 6.10 .Math. 10.sup.−8 (±0.88%) 1.69 .Math. 10.sup.−6 (±0.87%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 9.07 .Math. 10.sup.8 (±9.56%) no ohmic contact 1.35 .Math. 10.sup.4 (±1.70%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 21.38 (±13.5%) <0.25 ε.sub.r 3.64 (±6.24%) 2.62 (±7.18%) 2.97 (%15.7%) r + 1 4.67 (±2.12%) 17.0 (±16.9%) no TFLC μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) 3.37 .Math. 10.sup.−6 (±11.6%) Trapping Aging γ (cm.sup.1/2 .Math. V.sup.1/2) 1.95 .Math. 10.sup.−3 (±1.13%)

Reference Example IV

(124) Reference example IV relates to the use of bismuth(III) tris(3,5-difluorobenzoate), abbreviated to Bi(3,5-dfb).sub.3, as a metal complex for gas-phase deposition.

(125) Bi(3,5-dfb).sub.3 was synthesized in accordance with scheme 1. For Bi(3,5-dfb).sub.3, residues R.sup.A, R.sup.C and R.sup.E in scheme 1 are in each case hydrogen atoms and substituents R.sup.B and R.sup.D are in each case fluorine atoms.

(126) After purification by means of sublimation, it was confirmed by elemental analysis that Bi(3,5-dfb).sub.3 had been obtained (measured: carbon in %36.3; hydrogen in %1.4; calculated: carbon in %37.06; hydrogen in %1.32).

(127) FIGS. 15 and 16 and tables 10 and 11 summarize the electrical properties of organic layers doped with

(128) Bi(3,5-dfb).sub.3.

(129) Table 10: Summary of the electrical properties of i-TNata doped with Bi(3,5-dfb).sub.3

(130) TABLE-US-00010 TABLE 10 Summary of the electrical properties of 1-TNata doped with Bi(3,5-dfb).sub.3. (1:8) (1:4) (1:2) Exp. molar ratio 1/8.01 (4.77 .sub.vol. %) 1/3.93 (9.25 .sub.vol. %) 1/1.96 (17.01 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 4.27 .Math. 10.sup.−7 (±1.03%) 2.81 .Math. 10.sup.−7 (±0.66%) 2.97 .Math. 10.sup.−7 (±1.31%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 2.07 .Math. 10.sup.9 (±8.50%) 5.12 .Math. 10.sup.7 (±8.73%) 1.43 .Math. 10.sup.6 (±4.98%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r 2.67 (±7.01%) 2.60 (±9.36%) 2.69 (±10.8%) r + 1 6.46 (±2.28%) 3.75 (±3.36%) 1.56 (±1.90%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) 3.14 .Math. 10.sup.−5 (±11.9%) Ballistic γ (cm.sup.1/2 .Math. V.sup.1/2) 5.09 .Math. 10.sup.−4 (±1.16%)

(131) Table 11: Summary of the electrical properties of matrix materials i-TNata, α-NPB and spiro-TTB doped with

(132) (1:2) Bi(3,5-dfb).sub.3.

(133) TABLE-US-00011 TABLE 11 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(3,5-dfb).sub.3. 1-TNata α-NPB spiro-TTB Exp. molar ratio 1/1.96 (17.01 .sub.vol. %) 1/1.99 (24.64 .sub.vol. %) 1/2.00 (13.05 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 2.97 .Math. 10.sup.−7 (±1.31%) 7.18 .Math. 10.sup.−7 (±1.90%) 4.40 .Math. 10.sup.−6 (±1.73%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 1.43 .Math. 10.sup.6 (±4.98%) no ohmic contact 2.91 .Math. 10.sup.5 (±3.76%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 12.75 (±35.3%) <0.25 ε.sub.r 2.69 (±10.8%) 2.35 (±3.84%) Too conductive r + 1 1.56 (±1.90%) 12.9 (±21.4%) no TFLC μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) Ballistic Trapping Aging γ (cm.sup.1/2 .Math. V.sup.1/2)

Reference Example V

(134) Reference example V relates to the use of bismuth(III) tris(3,4,5-trifluorobenzoate), abbreviated to Bi(3,4,5-tfb).sub.3, as a metal complex for gas-phase deposition.

(135) Bi(3,4,5-tfb).sub.3 was synthesized in accordance with scheme 1. For Bi(3,4,5-tfb).sub.3, residues R.sup.A and R.sup.E in scheme 1 are in each case hydrogen atoms and the remaining substituents R.sup.B, R.sup.C and R.sup.D are in each case fluorine atoms.

(136) After purification by means of sublimation, it was confirmed by elemental analysis that Bi(3,4,5-tfb).sub.3 had been obtained (measured: carbon in %33.8; hydrogen in %1.2; calculated: carbon in %34.33; hydrogen in %0.82).

(137) FIGS. 17 and 18 and tables 12 and 13 summarize the electrical properties of organic layers doped with

(138) Bi(3,4,5-tfb).sub.3.

(139) Table 12: Summary of the electrical properties of i-TNata doped with Bi(3,4,5-tfb).sub.3.

(140) TABLE-US-00012 TABLE 12 Summary of the electrical properties of 1-TNata doped with Bi(3,4,5-tfb).sub.3. (1:8) (1:4) (1:2) Exp. molar rario 1/8.15 (5.59 .sub.vol. %) 1/3.92 (10.97 .sub.vol. %) 1/1.96 (19.73 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 6.45 .Math. 10.sup.−7 (±1.00%) 9.73 .Math. 10.sup.−7 (±0.88%) 1.09 .Math. 10.sup.−6 (±0.76%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 3.24 .Math. 10.sup.7 (±6.25%) 1.21 .Math. 10.sup.6 (±5.02%) 1.78 .Math. 10.sup.5 (±4.25%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r Too conductive r + 1 4.12 (±2.46%) 2.22 (±1.78%) 1.48 (±2.46%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) 6.13 .Math. 10.sup.−5 (±25%)* Ballistic γ (cm.sup.1/2 .Math. V.sup.1/2) 5.28 .Math. 10.sup.−4 (±1.6%)*

(141) Table 13: Summary of the electrical properties of matrix materials i-TNata, α-NPB and spiro-TTB doped with

(142) (1:2) Bi(3,4,5-tfb).sub.3.

(143) TABLE-US-00013 TABLE 13 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(3,4,5-tfb).sub.3. 1-TNata α-NPB spiro-TTB Exp. molar ratio 1/1.96 (19.73 .sub.vol. %) 1/2.00 (28.22 .sub.vol. %) 1/2.01 (15.23 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 1.09 .Math. 10.sup.−6 (±0.76%) 1.77 .Math. 10.sup.−6 (±1.68%) 1.19 .Math. 10.sup.−6 (±0.94%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 1.78 .Math. 10.sup.5 (±4.25%) 5.39 .Math. 10.sup.7 (±8.77%) 2.06 .Math. 10.sup.5 (±5.68%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r Too conductive 2.26 (±12.2%) Too conductive r + 1 1.48 (±2.46%) 3.28 (±2.22%) 3.28 (±3.72%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) Ballistic 9.39 .Math. 10.sup.−6 (±19.1%) 3.37 .Math. 10.sup.−3 (±23%)* γ (cm.sup.1/2 .Math. V.sup.1/2) 3.42 .Math. 10.sup.−3 (±3.90%) 2.01 .Math. 10.sup.−4 (±3.1%)*

Reference Example VI

(144) Reference example VI relates to the use of bismuth(III) tris(perfluorobenzoate), abbreviated to Bi(pfb).sub.3, as a metal complex for gas-phase deposition.

(145) Bi(pfb).sub.3 was synthesized in accordance with scheme 1. For Bi(pfb).sub.3, all five residues R.sup.A to R.sup.E in scheme 1 are in each case fluorine atoms.

(146) After purification by means of sublimation, it was confirmed by elemental analysis that Bi(pfb).sub.3 had been obtained (measured: carbon in %29.9(6); calculated: carbon in %29.93). FIGS. 19 and 20 and tables 14 and 15 summarize the electrical properties of organic layers doped with Bi(pfb).sub.3.

(147) Table 14: Summary of the electrical properties of 1-TNata doped with Bi(pfb).sub.3.

(148) TABLE-US-00014 TABLE 14 Summary of the electrical properties of 1-TNata doped with Bi(pfb).sub.3. (1:8) (1:4) (1:2) Exp. molar ratio 1/8.08 (5.18 .sub.vol. %) 1/3.98 (9.98 .sub.vol. %) 1/1.97 (18.28 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 9.81 .Math. 10.sup.−7 (±1.62%) 2.65 .Math. 10.sup.−6 (±1.73%) 6.06 .Math. 10.sup.−6 (±1.28%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 4.27 .Math. 10.sup.6 (±6.35%) 9.88 .Math. 10.sup.4 (±3.41%) 8.26 .Math. 10.sup.3 (±2.96%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r 2.92 (±4.86%) Too conductive r + 1 3.76 (±4.99%) 2.00 (±2.34%) no TFLC μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) Ballistic γ (cm.sup.1/2 .Math. V.sup.1/2)

(149) Table 15: Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with

(150) (1:2) Bi(pfb).sub.3.

(151) TABLE-US-00015 TABLE 15 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(pfb).sub.3. 1-TNata α-NPB spiro-TTB Exp. molar ratio 1/1.97 (18.28 .sub.vol. %) 1/2.00 (26.38 .sub.vol. %) 1/1.88 (14.90 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 6.06 .Math. 10.sup.−6 (±1.28%) 2.78 .Math. 10.sup.−6 (±0.96%) 9.52 .Math. 10.sup.−5 (±1.40%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 8.26 .Math. 10.sup.3 (±2.96%) 1.37 .Math. 10.sup.8 (±8.22%) 1.92 .Math. 10.sup.4 (±3.24%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r Too conductive 2.45 (±7.17%) Too conductive r + 1 no TFLC 4.97 (±2.34%) 2.98 (±1.77%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) Ballistic 4.88 .Math. 10.sup.−5 (±10.5%) Compliance γ (cm.sup.1/2 .Math. V.sup.1/2) 1.14 .Math. 10.sup.−3 (±0.84%)

Reference Example VII

(152) Reference example VII relates to the use of bismuth(II) tris(4-perfluorotoluate), abbreviated to Bi(4-pftl).sub.3, as a metal complex for gas-phase deposition.

(153) For Bi(4-pftl).sub.3, residues R.sup.A, R.sup.B, R.sup.D and R.sup.E in scheme 1 are in each case fluorine atoms and R.sup.C is a CF.sub.3 group.

(154) After purification by means of sublimation, it was confirmed by elemental analysis that Bi(4-pftl).sub.3 had been obtained (measured: carbon in %30.0; calculated: carbon in %29.03).

(155) FIGS. 21 and 22 and tables 16 and 17 summarize the electrical properties of organic layers doped with

(156) Bi(4-pftl).sub.3.

(157) Table 16: Summary of the electrical properties of i-TNata doped with Bi(4-pftl).sub.3.

(158) TABLE-US-00016 TABLE 16 Summary of the electrical properties of 1-TNata doped with Bi(4-pftl).sub.3. (1:8) (1:4) (1:2) Exp. molar ratio 1/8.10 (5.63 .sub.vol. %) 1/4.02 (10.75 .sub.vol. %) 1/1.97 (19.68 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 1.07 .Math. 10.sup.−6 (±0.81%) 2.62 .Math. 10.sup.−6 (± 0.89%) 4.13 .Math. 10.sup.−6 (±1.20%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 9.30 .Math. 105 (±3.67%) 2.31 .Math. 10.sup.5 (±3.03%) 3.83 .Math. 10.sup.4 (±2.85%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r Too conductive r + 1 2.44 (±29.0%) 1.77 (±2.86%) no TFLC μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) Ballistic γ (cm.sup.1/2 .Math. V.sup.1/2)

(159) Table 17: Summary of the electrical properties of matrix materials i-TNata, α-NPB and spiro-TTB doped with

(160) (1:2) Bi(4-pftl).sub.3.

(161) TABLE-US-00017 TABLE 17 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(4-pftl).sub.3. 1-TNata α-NPB spiro-TTB Exp. molar ratio 1/1.97 (19.68 .sub.vol. %) 1/2.04 (27.82 .sub.vol. %) 1/2.03 (15.13 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 4.13 10.sup.−6 (±1.20%) 3.20 .Math. 10.sup.−6 (±0.84%) 1.53 .Math. 10.sup.−4 (±1.02%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 3.83 .Math. 10.sup.4 (±2.85%) 3.41 .Math. 10.sup.6 (±3.72%) 1.25 .Math. 10.sup.4 (±3.93%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r Too conductive 2.10 (±27.4%) // r + 1 no TFLC 1.42 (±2.07%) 2.52 (±2.27%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) Ballistic Compliance γ (cm.sup.1/2 .Math. V.sup.1/2)

(162) Further conventional metal complexes with acetate- and trifluoroacetate-based ligands were also used by the inventors for comparison with the complexes used in the method according to the invention:

Reference Example VIII

(163) Reference example VIII relates to the use of bismuth(III) tris(trifluoroacetate), abbreviated to Bi(tfa).sub.3, as a metal complex for gas-phase deposition. Production is described in the literature (for example, Suzuki, H.; Matano, Y. in Organobismuth Chemistry, Elsevier 2001).

(164) FIGS. 23 and 24 and tables 18 and 19 summarize the electrical properties of organic layers doped with Bi(tfa).sub.3.

(165) Table 18: Summary of the electrical properties of i-TNata doped with Bi(tfa).sub.3.

(166) TABLE-US-00018 TABLE 18 Summary of the electrical properties of 1-TNata doped with Bi(tfa).sub.3. (1:8) (1:4) (1:2) Exp. molar ratio 1/8.24 (2.37 .sub.vol. %) 1/3.92 (4.85 .sub.vol. %) 1/1.97 (9.22 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 2.06 .Math. 10.sup.−6 (±0.95%) 4.47 .Math. 10.sup.−6 (±1.23%) 7.53 .Math. 10.sup.−6 (±1.21%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 6.82 .Math. 10.sup.5 (±3.31%) 2.10 .Math. 10.sup.4 (±2.34%) 9.40 .Math. 10.sup.3 (±2.50%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r Too conductive r + 1 2.45 (±1.50%) no TFLC no TFLC μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) After TFLC, the dope decreases to a limit near 3/2 (ballistic). γ (cm.sup.1/2 .Math. V.sup.1/2) Just before exponentially increasing (aging)

(167) “After TFLC, the slope decreases to a limit near 3/2 (ballistic)” and “Just before exponentially increasing (aging)” refers to a transition from one charge transport regime to another.

(168) Table 19: Summary of the electrical properties of matrix materials i-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(tfa).sub.3.

(169) TABLE-US-00019 TABLE 19 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(tfa).sub.3. 1-TNata α-NPB spiro-TTB Exp. molar ratio 1/1.97 (9.22 .sub.vol. %) 1/1.96 (14.21 .sub.vol. %) 1/1.97 (7.05 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 7.53 .Math. 10.sup.−6 (±1.21%) 3.97 .Math. 10.sup.−5 (±0.94%) 2.28 .Math. 10.sup.−4 (±0.79%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 9.40 .Math. 10.sup.3 (±2.50%) 3.80 .Math. 10.sup.4 (±2.13%) 1.05 .Math. 10.sup.4 (±3.03%) E.sub.bi (kV .Math. cm.sup.−1) <0.25 ε.sub.r Too conductive r + 1 no TFLC 2.50 (±2.54%) 2.58 (±2.99%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) Ballistic Aging γ (cm.sup.1/2 .Math. V.sup.1/2)

(170) It is apparent from the data that complexes with unfluorinated ligands also dope, but distinctly worse than complexes with fluorinated ligands. These complexes, like the other reference examples, are likewise unsuitable for sources in which collisions occur with at least one wall of the source.

Reference Example IX

(171) Reference example IX relates to the use of bismuth(III) tris(triacetate), abbreviated to Bi(ac).sub.3, as a metal complex for gas-phase deposition. The complex is commercially obtainable.

(172) FIGS. 25 and 26 and tables 20 and 21 summarize the electrical properties of organic layers doped with Bi(ac).sub.3.

(173) Table 20: Summary of the electrical properties of i-TNata doped with Bi(ac).sub.3.

(174) TABLE-US-00020 TABLE 20 Summary of the electrical properties of 1-TNata doped with Bi(ac).sub.3. (1:8) (1:4) (1:2) Exp. molar ratio 1/8.16 (1.46 .sub.vol. %) 1/4.20 (2.80 .sub.vol. %) 1/2.03 (5.64 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 4.31 .Math. 10.sup.−7 (±1.90%) 4.06 .Math. 10.sup.−7 (±0.86%) 6.13 .Math. 10.sup.−7 (±0.81%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) no ohmic contact 8.41 .Math. 10.sup.8 (±9.79%) 5.07 .Math. 10.sup.9 (±9.63%) E.sub.bi (kV .Math. cm.sup.−1) 3.13 (±100%) <0.25 ε.sub.r 2.67 (±37.3%) 2.10 (±10.4%) 2.78 (±6.88%) r + 1 9.87 (±2.98%) 5.70 (±2.73%) 7.31 (±1.24%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) 2.81 .Math. 10.sup.−5 (±42.0%) 5.12 .Math. 10.sup.−5 (±15.1%) 4.46 .Math. 10.sup.−5 (±11.8%) γ (cm.sup.1/2 .Math. V.sup.1/2) 1.29 .Math. 10.sup.−3 (±0.80%) 3.19 .Math. 10.sup.−4 (±1.88%) 6.76 .Math. 10.sup.−4 (±1.33%)

(175) Table 21: Summary of the electrical properties of matrix materials i-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(ac).sub.3.

(176) TABLE-US-00021 TABLE 21 Summary of the electrical properties of matrix materials 1-TNata, α-NPB and spiro-TTB doped with (1:2) Bi(ac).sub.3. 1-TNata α-NPB spiro-TTB Exp. molar ratio 1/2.03 (5.64 .sub.vol. %) 1/1.99 (8.99 .sub.vol. %) 1/2.05 (4.23 .sub.vol. %) σ.sub.0 (S .Math. cm.sup.−1) 6.13 .Math. 10.sup.−7 (±0.81%) 6.10 .Math. 10.sup.−10 (±16.0%) 1.68 .Math. 10.sup.−7 (±8.76%) ρ.sub.c.;0 (Ω .Math. cm.sup.−2) 5.07 .Math. 10.sup.9 (±9.63%) no ohmic contact E.sub.bi (kV .Math. cm.sup.−1) <0.25 16.3 (±10.8%) 18.4 (±12.9%) ε.sub.r 2.78 (±6.88%) 2.06 (±5.58%) 2.76 (±4.44%) r + 1 7.31 (±1.24%) 11.9 (±12.7%) 13.0 (±3.18%) μ.sub.0 (cm.sup.2 .Math. V.sup.1 .Math. s.sup.−1) 4.46 .Math. 10.sup.−5 (±11.8%) Trapping γ (cm.sup.1/2 .Math. V.sup.1/2) 6.76 .Math. 10.sup.−4 (±1.33%)

(177) The majority of the stated examples, example I and example II and most of the reference examples, have sufficiently good doping agent strengths. Matrix materials doped with these complexes exhibit sufficiently good electrical conductivities in the case of examples I and II and also of many reference examples.

(178) However, with regard to the stability, in particular the thermal stability, of the complex, only the metal complexes of example I and example II meet the elevated requirements for deposition by means of sources in which the complex collides with at least one wall of the source. In contrast, none of the complexes of the reference examples exhibited sufficient stability in order to be deposited from the gas phase by means of sources in which collisions occur with walls of the source.

(179) For example, only the complexes of example I and example II, but not the complexes of the reference examples, can be deposited by means of linear sources. While all the complexes are sufficiently stable for deposition by means of point sources, only those complexes with at least one substituent R.sup.1 thus meet the high stability requirements.

(180) The individual combinations of constituents and the features of the embodiments which have already been mentioned serve by way of example; exchanging and replacing such teaching with other teaching provided in the present document, including the cited documents, is likewise explicitly considered. A person skilled in the art will recognize that variations, modifications and other embodiments which are described here may likewise occur without deviating from or going beyond the concept and the scope of the invention.

(181) The above-stated description should accordingly be considered to be exemplary rather than limiting. The word “comprise” used in the claims does not exclude other constituents or steps. The indefinite article “a” does not exclude a plural meaning. The mere fact that certain measurements are recited in different claims does not mean that a combination of these measurements might not advantageously be used. The scope of the invention is defined in the following claims, and the associated equivalents.