KR101766709B1 - Organic semiconducting material and electronic component - Google Patents

Abstract

The present invention relates to an organic semiconductive material comprising at least one matrix material and at least one doping material, wherein the doping material is a [3] radialene compound and the matrix material is a terphenyl diamine compound, To form a doped semiconductor layer.

Description

TECHNICAL FIELD [0001] The present invention relates to organic semiconductive materials and electronic parts,

The present invention relates to an organic semiconductive material comprising at least one matrix material and at least one doping material, an organic component comprising such an organic semiconductive material, and at least one matrix material and at least one doping material for forming a doped semiconductor layer ≪ / RTI > The doping material is used to alter the electrical properties of the matrix material.

Over the years, the electrical conductivity of organic semiconductors has been known to be greatly affected by doping (electrical doping). Such organic semiconducting matrix materials can be formed from compounds having good electron donor properties or formed from compounds having good electron accepting properties. A strong electron acceptor such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluoro-tetracano-1,4-benzoquinodimethane (F4TCNQ) ) ≪ / RTI > (US 7074500). These form what is known as a " hole "in the electron-donor-like base material (hole transport material) as a result of the electron transport process, and the conductivity of the base material is the result of the number and mobility of the holes As shown in FIG. For example, N, N'-perylated benzidine (TPD) or N, N ', N "-perarylated starburst compounds such as the material TDATA, Metal phthalocyanines, especially phthalocyanine (ZnPc), for example, are known as matrix materials having hole transporting properties.

However, the above-mentioned compounds have disadvantages for technical applications in the production of doped semiconductive organic layers or corresponding electronic components including these types of doped layers, because the fabrication process or technical capacity in a high capacity production plant since the production process at the technical scale can not always be controlled sufficiently precisely, which leads to high control and regulatory efforts in the process to achieve the desired product quality, or to the undesired tolerance of the product, Lt; / RTI > There are also disadvantages in the use of previously known organic dopants in relation to electronic component structures such as light-emitting diodes (OLEDs), field-effect transistors (FETs) or solar cells, Because the cited production challenges that arise can cause irregularities that are not desired in electronic components or can cause undesired aging effects of electronic components. However, it should be noted at the same time that the doping agent used has a very high electron affinity (reduction potential) and other properties suitable for the application in question, since for example the doping agent also has a conductivity or conductivity of the organic semiconductive layer Because they determine other electrical properties at the same time. The energy positions of the HOMO of the matrix material and of the LUMO of the dopant are critical to the doping effect.

Electronic components including doped layers include, in particular, OLEDs and solar cells. OLEDs are known, for example, from US7355197 or US2009051271. Solar cells are known, for example, from US2007090371 and US2009235971.

It is an object of the present invention to provide an organic semiconductive material which substantially overcomes the disadvantages of the prior art. It is also intended to provide a mixture of a matrix material and a doping material for forming an improved organic component and a doped semiconductor layer. These objects are achieved by the features of independent claims 1, 6 and 11. Preferred embodiments will come from the dependent claims. In a particularly preferred embodiment, the use of N, N'-bis (phenanthrene-9-yl) -N, N'-bis (phenyl) -benzidine as matrix material is excluded.

According to a preferred alternative embodiment of the invention, the following layer sequences are provided in organic parts: (i) anode / dopant / HTM (HTM = hole transport material); (ii) Anode / dopant: HTM. In addition, the following sequence is preferred: (iii) dopant / HTM / EML or dopant / HTM / OAS; (iv) p-doped HTM / EML or dopant: HTM / OAS. The p-doped HTM is doped with a dopant according to the present invention. EML refers to an " emission layer "of an OLED, and an OAS refers to an " optical absorption layer of a solar cell" (typically a D-A heterojunction).

The layer sequences (i) to (iv) are also preferably a finite layer sequence.

In the literature, the doped hole transporting layer or materials for forming such a transporting layer focus either on the properties of the dopant or on the properties of the hole transporting material. The individual components are generally described with reference to the prior art. In practice, in general, better results are achieved in the case of parts that include a doped hole transport layer rather than a component having the same structure without a dopant in the hole transport layer. However, from this limited viewpoint, as a next step, it is overlooked that the hole transport material and the dopant are selectively configured with each other for complete optimization of the overall properties of the part. In particular, it is believed that the most suitable hole transport material for the doped layer will not function as well as the undoped hole transport material. Rather, dopants and matrices form a system that must be considered as a whole.

An important parameter for the hole transport material in the undoped layer is known as the "charge carrier mobility" for holes. This determines the extent to which the voltage drops across this layer when a particular current density flows through this layer. In an ideal scenario, the charge carrier mobility is high enough that the voltage drop across the individual layers is negligible compared to the voltage drop across the entire part. In this case, this layer is no longer limited to current flow and the charge carrier mobility can be considered to be sufficiently optimized.

In fact, this level has not yet been reached. In particular, in the case of a colorless hole transport material that does not cause absorption in the visible light spectrum range, a nominal voltage is required to induce current flow through the hole transport layer. This is especially true when the thickness of this layer is chosen not only to be minimized but also to have a certain minimum layer thickness (> 50 nm) for reasons of process-related reasons or part stability, for example. In this case, the selection of a good hole-transporting material for this layer must be directed primarily to the maximum charge-carrier transport, in order to limit the negative consequences for the performance parameters of the part. Other parameters that define the material, such as glass transition temperature (T _g ), processing properties, and material production cost, are relatively unimportant. For this reason, α-NPD (N, N'-bis (naphthalen-1-yl) -N, N'-bis (phenyl) -benzidine) having a very high charge carrier mobility has a relatively low glass Despite the transition temperature, it is one of the best hole transport materials. Accordingly, alpha -NPD is also used commercially to produce OLED products, which should be allowed, although a low glass transition temperature has been identified as a disadvantage of this approach.

This situation is different from the hole transport layer doped with the [3] radialene compound. The present inventors have found that the minimum voltage drop across the doped hole transport layer can be achieved in the case of a larger number of hole transport materials. [3] Due to the doping effect of the radialene compound, the layer is conductive. Conductivity is higher than the threshold value of 10 ^-5 S / cm for many hole transport materials. For this conductivity, only 0.1 V drops a relatively high current density of 100 mA / cm ² for a relatively high layer thickness of 100 nm. In particular, for OLED components having a typical operating voltage of at least 3V, this figure is less important. In this context it is to be noted that materials which have exhibited only unsatisfactory suitability in the undoped hole transport layer and thus are not conventionally used for the production of parts are included in the functional hole transport material in the doped hole transport layer It is important. It is also important to note that this environment opens up new possibilities for the selection of hole transport materials for doped hole transport layers.

The present inventors have discovered such hole transport materials exhibiting the best possible performance capability in the doped hole transport layer, and more particularly those hole transport materials in consideration of the hole transport material not considered in the conventional method.

As a result of these studies, it has been found that the best combination of [3] radialene compounds and hole transport materials is the best combination of [3] radialene compounds as the best hole transport materials (hole transport materials with high charge carrier mobility) ≪ / RTI > This is demonstrated by a practical example.

[3] Radialen  compound

Some preferred [3] radialenes which may advantageously be used for the purposes according to the invention are described below:

화학식 (1)

(1)

Wherein each R < ₁ > is independently selected from aryl and heteroaryl, wherein aryl and heteroaryl are at least partially, preferably all, substituted as electron-deficient groups (acceptor groups).

The aryl is preferably phenyl, biphenyl,? -Naphthyl,? -Naphthyl, phenanthryl or anthracyl.

Heteroaryl is preferably pyridyl, pyrimidyl, triazyl or quinoxalinyl.

The acceptor group is selected from an electron-attracting group, preferably fluorine, chlorine, bromine, CN, trifluoromethyl or nitro.

A general synthesis is described in "Preparation of the Oxocarbons, Pseudooxocarbon and Radialene Structures" in the patent application EP1988587.

Selection of matrix material

Suitable dopants for organic semiconductive materials such as hole transport materials HT, which are usually used in OLED or organic solar cells, are used in the present invention. The semiconducting material is preferably essentially hole-conducting. The following materials have been found to be able to be doped with the [3] radialene compound as a suitable matrix material.

Preferred are matrix materials selected from compounds of the formula:

화학식 (2)

(2)

Wherein R ₁ to R ₁₈ are each independently selected from H and alkyl (C ₁ -C ₉ , branched or unbranched).

A material selected from two of the following formulas is also preferred:

Wherein R ₁ to R ₁₃ are H and alkyl (C ₁ -C ₉ , branched or unbranched)

Wherein R ₁ to R ₁₄ are H and alkyl (C ₁ -C ₉ , branched or unbranched)

The materials of the following formulas (3), (4), (5) and (6) are also preferred. The matrix material of formula (3) is particularly preferred.

화학식 (3)

(3)

화학식 (4)

(4)

화학식 (5)

(5)

화학식 (6)

(6)

The following compounds are preferred: HTM of Formula 3, HTM of Formula 4, HTM of Formula 5, HTM of Formula 6. The HTM of formula (3) is the best material.

Also preferred is a matrix material selected from formula (3) in which at least one H in formula (3) is replaced by an aromatic compound and / or a heteroaromatic compound and C ₁ -C ₂₀ alkyl.

Wherein the matrix material is a material of HTM of Formula 4, HTM of Formula 5, HTM of Formula 6 and the dopant is 2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- -Cyanotetrafluorophenyl) acetonitrile) doped HTL (hole transport layer) is also preferable.

Wherein the matrix material is HTM of Formula 3 and the doping agent is 2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (p-cyanotetrafluorophenyl) acetonitrile) A doped HTL is also preferred.

The present invention forms a doped HTL with low absorption, improved conductivity and / or improved thermal stability. In general, improved overall performance is achieved compared to alpha -NPD.

1a shows a schematic illustration of a doped hole transport layer 12 on a substrate 11 wherein the hole transport layer 12 is in electrical contact with two electrodes 13 and 14. [ Accordingly, the planar structure is used as, for example, a resistor, a conductive pathway, or the like.
Figure IB shows a schematic illustration of a doped hole transport layer 17 between two electrodes 16 and 17 on a substrate 15. [ Additional layers 18 may be provided. Such a laminated structure is used, for example, in an OLED, an organic solar cell, or the like.
Fig. 2 shows an example of a diode characteristic curve.

Electronic parts

A number of electronic components or devices comprising such components can be produced by using organic compounds according to the present invention to form doped organic semiconductive materials that can be arranged in particular in the form of layers or electrically conductive paths have. In particular, the doping material (doping material) can be used in an organic light emitting diode (OLED), an organic solar cell, an organic diode, and in particular a high rectification such as 10 ³ to 10 ⁷ , preferably 10 ⁴ to 10 ⁷ or 10 ⁵ to 10 ⁷ ratio, or may be used to produce an organic field-effect transistor. Improved conductivity of the doped layer and / or charge carrier implantation of the contact in the doped layer can be improved by the dopant according to the present invention. Particularly in the case of an OLED, the part may have a pin structure or an inverted structure, but is not limited to this structure. However, the use of a dopant according to the present invention is not limited to the above-described advantageous representative embodiments. OLEDs free of ITO (indium tin oxide) are preferred. Also, an OLED having at least one organic electrode is also preferred. (A) The preferred organic electrode (s) are conductive layers containing the following materials as major constituents: PEDOT-PSS, polyaniline, carbon nanotubes, graphite.

A typical structure of a standard OLED can be considered as follows:

1. Carriers, substrates, for example, glass,

2. Electrode, hole-injected (anode = anode terminal), preferably transparent, for example indium tin oxide (ITO) or FTO (Braz. J. Phys. )),

3. Hole injection layer,

5. A hole-side blocking layer for preventing exciton diffusion from the emission layer and preventing charge carrier leakage from the emission layer,

6. CBP containing a luminescent layer or a multilayer system contributing to luminescence, for example an emitter mixture (for example phosphorescent triplet emitter iridium-tris-phenylpyridine Ir (ppy) 3) Alq3 (tris-quinolinato aluminum) mixed with emitter molecules (for example, fluorescent single-emitter coomarin)

7. An electron-side barrier layer, for example BCP (bathocuproine), for preventing exciton diffusion from the emissive layer and preventing charge carrier leakage from the emissive layer,

8. Electron transport layer (ETL), for example BPhen, Alq3 (tris-quinolinato aluminum),

10. Electrode, usually a metal with low work function, electron-injection (cathode = cathode terminal), for example aluminum.

Of course, the layers can be omitted or one layer (or one material) can fulfill a plurality of properties, for example layers 3 to 5, or layers 7 and 9 can be combined. Additional layers may also be used. Laminated OLEDs are also intended and included.

This structure describes the non-inverted structure (anode on the substrate) of the OLED that emits (bottom emission) on the substrate side. There are a variety of concepts describing OLEDs emanating from a substrate (DE 102 15 210.1), all of which are reflective (and transparent in the case of transparent OLEDs) substrate-side electrodes (the anode in the non- It shares a common feature that the electrodes are (semi-transparent). When the order of the layers is reversed (cathode on the substrate), the reversed OLED is referenced (see DE 101 35 513.0). Also, in this case, if a particular measure can not be obtained, a performance loss will be expected.

A preferred design of the OLED structure according to the present invention is a reversed structure (where the cathode is present on the substrate), and light is emitted through the substrate. It is also desirable if the OLED is top emitting.

A typical structure of an organic solar cell can be considered as follows:

1. Carriers, substrates, such as glass,

2. An anode, preferably a transparent anode, for example indium tin oxide (ITO),

3. Hole injection layer,

5. A hole-side intermediate layer, preferably a barrier layer, for preventing exciton diffusion from the absorber layer (referred to as the optically active layer or emissive layer) and preventing charge carrier leakage from the emissive layer,

6. An optically active layer (absorption layer), a strong light-absorbing layer usually formed of heterojunction (two or more layers or mixed layers), for example a mixed layer formed of C60 and ZnPc,

7. Electron transport layer,

10. Cathode, for example aluminum.

Of course, the layers may be omitted, or one layer may satisfy a plurality of properties. Additional layers may also be used. Laminated (tandem) solar cells are also contemplated and included. Transform solar cells, inverted solar cells or m-i-p solar cells are also possible.

The preferred design of the solar cell structure is a reversed structure (where the cathode is present on the substrate), and light enters through the substrate.

Another desirable design of the solar cell structure is a reversed structure (where the cathode is present on the substrate), and light enters through the anode.

Example

The invention will be explained in more detail on the basis of some embodiments.

[3] Radialen  Synthesis of compounds

A solution of 207 mmol cyanoacetic acid ester in 50 ml dimethylformamide was added dropwise to a solution of 207 mmol starting material (a-e) and 250 mmol potassium carbonate in 370 ml dimethylformamide with stirring. The mixture was stirred at room temperature for 48 hours. Thereafter, the mixture was added to 1 L of ice water. The solution was vigorously stirred and mixed with 100 ml of concentrated acetic acid. This aqueous solution was then extracted four times with chloroform. Thereafter, the purified organic phase was dried with magnesium sulfate and then completely concentrated under vacuum. The raw product was used in the next synthesis without further purification.

The total amount of the aryl cyanoacetic acid ester (f-j) was heated under reflux in 84 ml acetic acid (50%) with 4.15 ml concentrated sulfuric acid for 16 hours. After cooling, the total amount was added to 120 ml ice water and stirred for 30 minutes. The phases were separated and the aqueous phase was extracted with 100 ml chloroform. The purified organic phase was washed with 100 ml of water and then with 100 ml of a saturated sodium bicarbonate solution. After drying with magnesium sulfate and removal of the solvent, a colorless oil (k-o) was obtained after distillation under vacuum.

Lithium hydride (98%) was suspended in 600 ml glyme and cooled to 0 < 0 > C. 152 mmol of aryl acetonitrile (k-o) was slowly added dropwise to 60 ml of glyme. The ice bath was removed and the mixture was allowed to warm to room temperature. After stirring at room temperature for 15 minutes, the mixture was again cooled to 0 < 0 > C and 40.0 mmol tetrachloropropene in 40 ml glime was slowly added dropwise. After warming to room temperature, the mixture was stirred for an additional 44 hours. The mixture was then added to 1.2 L ice water and acidified using hydrochloric acid (pH = 1). The aqueous solution was each shaken three times with 500 ml ethyl acetate and the purified organic phase was washed first with saturated saline, then with water, then with sodium carbonate solution and finally with water again. This was dried with magnesium sulfate and the solvent was removed in vacuo. The residual dark brown oil was used in the next synthesis without further purification.

The material was dissolved in 1.4 l acetic acid and mixed dropwise with a pre-prepared mixture formed with 360 ml hydrobromic acid (48%) and 120 ml nitric acid (65%) with stirring. This was stirred for 1.5 hours and then filtered. The red solid was washed with water, dried in vacuo and then purified by gradient sublimation (p-t).

HTM Synthesis of

Examples of HTM of formula (3)

70 g (0.14 mol) of 4,4 "-diiodoterphenyl, 140 g (0.44 mol) bis- (biphenylyl) -amine, 45 g Potassium carbonate, 220 ml of Marlotherm and 0.3 ml of toluene. The mixture was heated to 110 < 0 > C and 20 g copper catalyst was added. The mixture was heated to a temperature of approximately 195 ° C within 3.5 hours. This temperature was maintained for 42 hours. Thereafter, the batch was cooled to 90 DEG C and an inorganic component was discharged using a suction filter. 100 ml of methanol was added and the product was removed under vacuum using a suction filter. The product was then recrystallized with 2 L dimethylformamide. After removing the recrystallized product, it was washed again with 200 ml of methanol to remove the encapsulated dimethylformamide.

83 g of product was obtained after drying at 100 deg.

How to measure

The conductivity of the thin-layer sample was measured using the two-point method. In this case, contacts made from a conductive material such as gold or indium tin oxide were applied to the substrate. The thin layer to be tested subsequently was immersed over a large area of the substrate so that the contacts were covered by a thin layer. After the voltage was applied to the contact, the flowing current was measured. Thereafter, the conductivity of the thin layer material was determined from the resistance values obtained on the basis of the outer shape of the contacts and the layer thickness of the sample. Two-point methods are allowed where the resistance of the thin layer is significantly greater than the resistance or contact resistance of the supply line. This is experimentally confirmed by providing a sufficiently large contact gap, thus demonstrating the linearity of the current-voltage characteristic curves.

The thermal stability can be determined using the same method and the same structure by progressively heating the (doped or undoped) layer and measuring its conductivity after a rest period. The maximum temperature at which the layer can be maintained without losing the desired semiconductive properties is the temperature just before the conductivity is lost. For example, the doped layer can be heated on the substrate with two adjacent electrodes, increasing by 1 DEG C, as described above, with a 10 second waiting interval between each increase. Thereafter, the conductivity is measured. Conductivity changes with temperature, and in the case of a certain temperature, it disappears rapidly. Thus, the thermal stability provides a temperature below the temperature at which the conductivity is not abruptly lost.

Doping concentration

The doping agent preferably has a doping concentration of 1: 1 or less, preferably 1: 2 or less, more preferably 1: 5 or less, or 1: 10 or less, Or less. The doping concentration may be limited to a range of 1: 5 to 1: 10000.

Doping procedure

Doping of the individual matrix materials with the p-doping agent used according to the invention can be carried out in one or a combination of the following steps:

a) mixed evaporation with one source for the matrix material and one source for the dopant under vacuum;

b) doping the matrix layer with a solution of the p-dopant followed by evaporation of the solvent, especially evaporation of the solvent by heat treatment

c) surface doping of the matrix material layer by a layer of a dopant applied to the surface thereof

d) preparing a solution of the matrix molecules and the dopant, followed by formation of a layer from this solution by conventional means, for example evaporation or spin-coating of the solvent.

In this way, it is possible according to the invention to form p-doped layers of organic semiconductors which can be used in various ways.

Conductivity measurement

Doped semiconductor layer - Example 1:

A 50 nm thick layer of HTM of Formula 3 was doped with compound (p). The doped layer was formed under high vacuum by mixed evaporation of the HTM of formula (3) and the dopant (p). The concentration of the dopant in the matrix was 3 mol%. The evaporation temperature of the dopant is 372 ° C. The doped layer showed a high conductivity of 6 · 10 ^-4 S / cm. The thermal stability of the layer was 133 deg.

part: Example  One:

A layer of HTM of Formula 3 was doped with compound (p). The doped layer was deposited on a glass substrate coated with ITO by means of mixed evaporation of HTM of formula (3) with a dopant (p) under high vacuum. The concentration of the dopant in the matrix is 1.5; 3.0; 4.5% by weight. Also, an α-NPD layer doped with 3% by weight of the compound (p) was immersed on the same substrate as a reference example. Thereafter, a layer of alpha -NPD, a fluorescent blue emitter layer, undoped ETL and blocking layer, and an n-doped electron transport layer, and an aluminum cathode were deposited while maintaining vacuum. Thereafter, the parts processed in this way were protected from water by encapsulating in advance with the appropriate getter-introduced covering glass.

Thus, a blue OLED emitting through a glass substrate was produced, and the characteristic data of the OLED was summarized in the following table.

From the above table, it can be seen that the working voltage using the HTM of formula (3) is improved as compared to? -NPD. This lower initial voltage also results in better efficiency. For example, in the case of the reference example, the power efficiency of 10.18 was improved to 10.72 lm / W using the HTM of formula 2, where both HTM and alpha -NPD were doped with 3 wt% (p) . As a result, the improvement in efficacy exceeds 5%. Another important performance parameter for OLED components is the service life, defined as the length of time until the initial brightness at a particular current density drops to half. From the above table it can be seen that also in this case, no loss is retained when using the HTM of formula (3) relative to? -NPD. Conversely, the service life at 30 mA / cm < 2 > is improved by more than 15% from 476 to 556 h in the above example with 3 wt% electrical doping.

Example 2

A layer of HTM of Formula 3 was doped with compound (p). The doped layer was deposited on a glass substrate coated with ITO by means of mixed evaporation of HTM of formula (2) with a dopant (p) under high vacuum. The concentration of the dopant in the matrix was 3.0 wt%. Also, an α-NPD layer doped with 3% by weight of the compound (p) was immersed on the same substrate as a reference example. Thereafter, a layer of alpha -NPD or a layer of HTM of Formula 3 was deposited while maintaining the vacuum. The parts were completed with a fluorescent red emitter layer, an undoped ETL layer and a blocking layer, and an n-doped electron transport layer and an aluminum cathode. Thereafter, the parts worked in this way were protected from water by encapsulating in advance with the appropriate getter-introduced covering glass.

Thus, a red OLED emitting through a glass substrate was produced, and the characteristic data of the OLED was summarized in the following table.

From the above table it can be seen that the effectiveness of the red OLED is significantly improved when using the HTM of formula 3 as a doped and undoped layer compared to a reference OLED, . In this particular case, the power efficacy has been improved from, for example, 7.8 to 8.4 lm / W, resulting in an improvement of approximately 8%.

Example 3:

Other component examples demonstrate the surprising thermal stability of the doped semiconductor layer. To this end, a layer of HTM of Formula 4, HTM of Formula 5, and a 30 nm thick layer of HTM of Formula 6 were respectively processed on ITO glass. A reference layer of 30 nm α-NPD was also applied. All of these materials were electrically doped to 3% (p) by coevaporation. A uniform layer of 50 nm thick, highly stable hole-transporting material TBRb (tert-butyl rubrene) was evaporated as an additional resist on all these layers. The hole-transport components were terminated with a common aluminum electrode 100 nm thick. Thereafter, the parts worked in this way were protected from water by encapsulating in advance with the appropriate getter-introduced covering glass.

The current-voltage characteristic curves of the parts thus obtained were measured. To estimate the thermal stability, all OLEDs were heated to 120 ° C for 1 hour in the furnace. After cooling to room temperature, the current-voltage characteristic curve was again measured. The obtained diode characteristic curve is shown in FIG. 2, where (21) represents the HTM of the formula (6), (22) represents the HTM of the formula (5), (23) , And (24) represent the IV data of? -NPD.

The characteristic curves can largely be divided into a desired forward current in the case of a voltage higher than 1V and a parasitic leakage current in the case of a voltage of less than 1V. In this case, 1V is the turn-on voltage of the part. It can be clearly seen that the α-NPD component has a very high leakage current even after the processing as compared with the material according to the present invention, the HTM of the formula 3, the HTM of the formula 4, the HTM of the formula 5 and the HTM of the formula 6 . For example, the difference at -5 V is approximately 100 times. The problem of parasitic leakage current is further magnified for α-NPD after heating. In this case, the leakage current reaches almost 10 mA / cm < ² > at -5V. On the other hand, parts using the hole transport layer according to the present invention are highly resistant to temperature increase at -5 V and exceed five digits above the reference value of? -NPD at approximately 0.0001 mA / cm ² . The present embodiment shows that highly thermally stable organic components can be produced when using the hole transporting material according to the present invention rather than using the standard hole transporting material? -NPD.

Example 4:

Four layers of HTM (see table below) were doped with compound (p). The doped layer was deposited under high vacuum on a glass substrate coated with ITO by mixed evaporation with a dopant (p). The concentration of the dopant in the matrix was 3.0 wt% in each of the four cases. Also, an α-NPD layer doped with 3% by weight of the compound (p) was immersed on the same substrate as a reference example. Subsequently, a layer of? -NPD, a red-, yellow-, blue- and green-emitting layer, an undoped ETL, and a blocking layer, an n-doped electron transport layer and an aluminum cathode were deposited while maintaining vacuum. Thereafter, the parts worked in this way were protected from water by encapsulating in advance with the appropriate getter-introduced covering glass.

The processed OLED thus emits on-white light with a color coordinate of (0.39, 0.40). The corresponding characteristic data are summarized in the following table.

From the above table, it can be seen that the initial efficacy of the components according to the use of the hole transport layer according to the present invention is somewhat better and some somewhat poorer than the standard hole transport material α-NPD. On the other hand, a considerable improvement is achieved in relation to the service life of the components according to the above definition measured at 85 캜. The latter is improved, for example, by up to 35% when the HTM of formula (6) is used.

The features of the invention described in the foregoing description, the claims, and the drawings may be essential to both the individual and any combination in the practice of the invention in its various embodiments.

Claims (17)

An organic semiconducting material comprising at least one matrix material and at least one doping material,
Wherein the doping material is selected from compounds of formula (1)
Wherein the matrix material is selected from compounds of formula (2): < EMI ID =

(1)
Wherein R ₁ is independently selected from aryl and heteroaryl, wherein the aryl and heteroaryl are substituted with one or more electron-poor substituents;

(2)
Wherein R ₁ to R ₁₈ are each independently selected from H and alkyl, wherein the alkyl may be branched or unbranched. The organic semiconducting material according to claim 1, wherein the aryl and heteroaryl are completely replaced by an electron-poor substituent. The organic semiconducting material according to claim 1, wherein the alkyl is C ₁ -C ₉ alkyl. The organic semiconducting material of claim 1, wherein the doping material is incorporated into the matrix material. The organic semiconducting material of claim 1, wherein the doping material and the matrix material form two layers in contact. The organic semiconductive material according to claim 1, wherein the doping material and the matrix material are mixed with each other. The method of claim 1,
2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (perfluorophenyl) -acetonitrile);
2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (perfluoropyridin-4-yl) -acetonitrile);
2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (4-cyanopiperophenyl) -acetonitrile);
2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (2,3,5,6-tetrafluoro-4- (trifluoromethyl) Acetonitrile); and
(2,2-dichloro-3,5-difluoro-4- (trifluoromethyl) phenyl) ) -Acetonitrile. ≪ / RTI > An organic component comprising an organic semiconductive material according to any one of claims 1 to 7. The organic component according to claim 8, characterized by being a light emitting component. The organic component according to claim 8, characterized in that it is an organic solar cell. 11. The organic component according to claim 10, wherein the cathode of the organic component is closer to the substrate of the organic component than the anode of the organic component. 12. The organic component of claim 11, wherein the cathode is transparent and the substrate and / or anode is reflective. A mixture comprising at least one matrix material and at least one doping material for forming a doped semiconductor layer,
Wherein the doping material is selected from compounds of formula (1)
Characterized in that the matrix material is selected from compounds of the formula (2)

(1)
Wherein R ₁ is independently selected from aryl and heteroaryl, wherein the aryl and heteroaryl are substituted with one or more electron-poor substituents,

(2)
Wherein R ₁ to R ₁₈ are each independently selected from H and alkyl, wherein the alkyl may be branched or unbranched. 14. The mixture of claim 13, wherein the aryl and heteroaryl are fully substituted by an electron-poor substituent. 14. The method of claim 13, wherein the mixture, characterized in that the alkyl is C ₁ -C ₉ alkyl. 14. The method of claim 13 wherein the matrix material is selected from the group consisting of N4, N4, N4 ", N4 "-tetra ([1,1'-biphenyl] ] -4,4 "-diamine. 15. The method of claim 13 or 14,
2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (perfluorophenyl) -acetonitrile);
2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (perfluoropyridin-4-yl) -acetonitrile);
2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (4-cyanopiperophenyl) -acetonitrile);
2,2 ', 2 "- (cyclopropane-1,2,3-triylidene) tris (2- (2,3,5,6-tetrafluoro-4- (trifluoromethyl) Acetonitrile); and
(2,2-dichloro-3,5-difluoro-4- (trifluoromethyl) phenyl) ) -Acetonitrile). ≪ / RTI >

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