CN113161486B - P-type organic thin film transistor based on molybdenum trioxide contact doping and preparation method - Google Patents

P-type organic thin film transistor based on molybdenum trioxide contact doping and preparation method Download PDF

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CN113161486B
CN113161486B CN202110370278.8A CN202110370278A CN113161486B CN 113161486 B CN113161486 B CN 113161486B CN 202110370278 A CN202110370278 A CN 202110370278A CN 113161486 B CN113161486 B CN 113161486B
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李文武
姬韵博
黄凡铭
陆定一
褚君浩
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East China Normal University
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Abstract

The invention discloses a molybdenum trioxide contact doping-based P-type organic thin film transistor and a preparation method thereof. Firstly, preparing a layer of gold on an insulating substrate through a mask as a source electrode and a drain electrode, then preparing a layer of molybdenum trioxide on a gold electrode as a contact doping layer, then forming a P-type organic semiconductor active layer on the surface of a sample with a prepared electrode by using a sol-gel method, spin-coating a layer of dielectric material on the active layer as an insulating layer, and finally preparing an aluminum gate electrode on the surface of the insulating layer through the mask. Compared with the traditional organic thin film transistor, the molybdenum trioxide contact doped organic thin film transistor prepared by the method has the advantages that the carrier mobility and the device on-off ratio are obviously improved, and the sub-threshold swing amplitude and the threshold voltage of the device are greatly reduced. The invention improves the electrical property of the P-type organic thin film transistor with the top-gate bottom-contact structure and has the characteristics of low cost and simple process steps.

Description

P-type organic thin film transistor based on molybdenum trioxide contact doping and preparation method
Technical Field
The invention relates to the fields of microelectronic materials and device technology, information display and the like, in particular to a P-type organic thin film transistor based on molybdenum trioxide contact doping and a preparation method thereof.
Background
Organic electronic flexible devices have received extensive attention from academia and social industries during the last 30 years, and are an important development direction of future flexible electronic display devices, especially during the last 5-10 years, organic electronics has made a long-term progress in a plurality of application fields, such as organic field effect transistors, organic solar cells, biosensors, TFT arrays, organic light emitting diodes, and the like. At present, organic materials and devices are gradually industrialized from basic research, and have the characteristics of simple manufacturing process, flexibility, diversity, low cost and the like in application and production; along with the reduction of the processing temperature of the device, the energy consumption required in the preparation process is reduced, so that the great advantage is highlighted in flexible display; in the future, the size of the OTFT device can be made smaller, the integration level is higher, and the operation rate and the calculation processing capacity of the OTFT device can be greatly improved. Organic thin film transistors have become an important research area with rapid development and bright future. However, the low field effect mobility has been a major problem that severely hampers the performance of organic thin film transistors, as compared to conventional silicon-based transistors, which has greatly limited the large-scale commercial application of organic thin film transistors.
Since the quality of the interface between the metal and the organic semiconductor active layer at the source and drain electrodes of the organic thin film transistor directly affects the injection and collection processes of carriers, the contact interface between the electrode and the semiconductor layer needs to be optimized as much as possible in order to improve the mobility of the organic semiconductor. However, even if gold having a large work function is used as the metal electrode, the gold electrode without modification still has a certain schottky barrier height, which hinders carrier transport. In addition, for the preparation process of the common P-type organic semiconductor active layer, a directional brush coating method, a magnetic field induced arrangement method, a single-molecule self-assembly layer introduction method and other complex and expensive methods are adopted, the surface of the prepared organic semiconductor active layer has more defects, the surface roughness is larger, the carrier transmission is seriously influenced, the mobility is lower, and further, the ideal electrical performance of the transistor cannot be obtained.
Therefore, it is desirable to provide a method for improving the field effect mobility of P-type organic thin film transistors with high efficiency.
Disclosure of Invention
In view of the above, the present invention provides a P-type organic thin film transistor based on molybdenum trioxide contact doping and a method for fabricating the same. The P-type organic thin film transistor applicable to the preparation method is of a top-gate-bottom contact structure, and the transistor sequentially comprises a gate electrode, a dielectric layer, a P-type semiconductor active layer, a molybdenum trioxide contact doping layer, a source/drain electrode and a substrate from top to bottom. According to the method, after the preparation of the source/drain electrode of the P-type organic thin film transistor is finished, a contact doping layer is formed on the surface of the source/drain electrode in a mask alignment mode, the contact doping of the P-type organic thin film transistor is realized through the contact doping layer, the contact between a P-type organic semiconductor active layer and a gold electrode is optimized, and the electrical property of the P-type organic thin film transistor is improved.
The specific technical scheme for realizing the purpose of the invention is as follows:
a preparation method of a P-type organic thin film transistor based on molybdenum trioxide contact doping comprises the following specific steps:
step 1: preparation of the solution
A1: preparation of semiconductor solution
Preparing a P-type organic semiconductor material and an organic solvent according to the mass-volume ratio of 8 mg/ml; wherein the P-type organic semiconductor material is: a polymer of 1, 4-dioxodipyrrole and thiophene, DPPT-TT; the organic solvent is chlorobenzene or p-dichlorobenzene;
a2: preparation of insulating layer solution
Preparing an insulating layer material and a high-solubility organic solvent according to the mass-volume ratio of 80 mg/ml; wherein the insulating layer is made of high molecular polymer; the high-solubility organic solvent is acetic acid or butyl acetate;
a3: dissolution of the solution
Respectively placing the prepared semiconductor solution and the insulating layer solution on a heating plate, standing and dissolving for 24 hours at 60 ℃;
step 2: preparation of devices
B1: cleaning of substrates
Selecting an insulating substrate, sequentially placing the substrate in deionized water, acetone and alcohol, respectively cleaning for 15 minutes by using an ultrasonic cleaning machine, and then drying by using a nitrogen gun;
b2: preparation of source-drain electrode
The vacuum thermal evaporation coating technology is adopted, gold particles are placed on a first thermal evaporation boat, and a mechanical pump and a molecular pump are used for pumping the vacuum 10 in a thermal evaporation cavity -5 ~10 -4 Pa, evaporating gold with the thickness of 30nm on the substrate by using a stainless steel mask plateIs a source/drain electrode; wherein the thermal evaporation current is 100-160A, and the speed is 0.01-0.05 nm/s;
b3: preparation of contact doped layer
Spreading molybdenum trioxide crystal powder on a second thermal evaporation boat by adopting a vacuum thermal evaporation coating technology, and pumping the thermal evaporation chamber to vacuum 10 by using a mechanical pump and a molecular pump -5 ~10 -4 A stainless steel mask is utilized to evaporate molybdenum trioxide with the thickness of 2-5nm on the surface of the source and drain electrodes at the same position to serve as a contact doping layer under the Pa condition, and when the thickness of the molybdenum trioxide is very thin (<1 nm) and the contact doping layer is a discontinuous thin film, which can result in poor device performance when the thickness of the contact doping layer is too high (b:)>6 nm), the low conductivity and bulk resistance of the material itself become gradually apparent, which also results in the performance degradation of the device; wherein the thermal evaporation current is 60-75A, and the speed is 0.01-0.02 nm/s;
b4: preparation of semiconductor thin films
Spreading the prepared semiconductor solution on the upper surface of the substrate by a liquid transfer gun, and spin-coating for 5 seconds at the rotating speed of 500rpm by using a spin coater, and then spin-coating for 40-80 seconds at the rotating speed of 2000 rpm; placing the sample on a heating plate to be heated and annealed at 200 ℃ for 45 minutes in a pure argon environment, wherein the semiconductor layer is coated in a spinning mode in the step; the thickness range of the prepared semiconductor film is 35-45nm, and the semiconductor film is the active layer.
B5: preparation of insulating layer film
Spreading the prepared insulating layer solution on the upper surface of the semiconductor film by a liquid transfer gun, and homogenizing for 5 seconds at the rotating speed of 500rpm and then 60 seconds at the rotating speed of 2000rpm by a spin coater; placing the sample with the insulating layer coated in a spinning mode in the step on a heating plate in a pure argon environment, and heating and annealing the sample for 2 hours at the temperature of 80 ℃;
b6: preparation of grid electrode
And through the calibration of an optical microscope, enabling the opening position of the stainless steel mask plate to correspond to a channel between the source electrode and the drain electrode, and preparing aluminum with the thickness of 60nm on the upper surface of the insulating layer by utilizing a vacuum thermal evaporation coating technology to serve as a gate electrode to obtain the molybdenum trioxide contact doped P-type organic thin film transistor.
In the step A2, the high molecular polymer is polystyrene and has a contact angle of at least 90 degrees with water.
In step B1, the insulating substrate is glass, silicon dioxide, or poly-p-phthalic plastic.
The P-type organic thin film transistor based on molybdenum trioxide contact doping is prepared by the method.
Compared with the traditional organic thin film transistor, the organic thin film transistor prepared by the invention has the advantages that the carrier mobility of the device is obviously improved, and the sub-threshold swing amplitude and the threshold voltage of the device are greatly reduced. The invention improves the electrical property of the P-type organic thin film transistor with the top-gate bottom-contact structure, and has the characteristics of low cost, simple process steps and wide application in the P-type organic thin film transistor.
Drawings
FIG. 1 is a schematic cross-sectional structure of a P-type organic thin film transistor of a comparative example;
FIG. 2 is a schematic cross-sectional view of a P-type organic thin film transistor according to the present invention;
fig. 3 is a graph comparing transfer characteristics of P-type organic thin film transistors prepared in comparative example and example.
Detailed Description
According to the invention, a dense molybdenum trioxide contact doping layer with controllable thickness is prepared on the upper surface of the electrode under the self-alignment of the mask plate through a traditional electrode preparation process. Molybdenum trioxide can effectively reduce the Schottky barrier height formed by the contact of a source electrode, a drain electrode and a P-type organic semiconductor due to the higher work function of the molybdenum trioxide, is beneficial to the transmission of holes between interfaces, and can be used as a hole transmission layer to carry out hole doping on a semiconductor active layer on the premise of not damaging the molecular structure of the semiconductor active layer, thereby influencing the electron hole capturing process, effectively reducing the contact type recombination of electrons and holes, increasing the carrier concentration in a P-type organic semiconductor film channel, obviously improving the mobility of the P-type organic film transistor and obviously reducing the subthreshold swing and the threshold voltage of the P-type organic film transistor. Therefore, the invention can greatly improve the electrical property of the P-type organic thin film transistor.
The invention is further explained below with reference to the drawings and the embodiments.
The following description of the preferred embodiments of the present invention is provided for illustration, but should not be construed as limiting the invention to the embodiments set forth herein, and all equivalent changes and modifications that fall within the spirit and scope of the present invention are intended to be embraced therein.
Fig. 2 is a schematic illustration of an embodiment of the invention, which should not be construed as being limited to the particular shapes of regions illustrated in the figures. In the present embodiment, all are represented by rectangles, and the representation in the figures is schematic, but this should not be construed as limiting the scope of the invention.
Comparative example
Undoped traditional P-type organic thin film transistor preparation
A1: preparation of semiconductor solution
Preparing a P-type organic semiconductor material and an organic solvent according to the mass-volume ratio of 8 mg/ml; wherein the P-type organic semiconductor material is: a polymer of 1, 4-dioxodipyrrole and thiophene, DPPT-TT; the organic solvent is p-dichlorobenzene;
a2: preparation of insulating layer solution
Preparing an insulating layer material and a high-solubility organic solvent according to a mass-volume ratio of 80 mg/ml; wherein the insulating layer material is Polystyrene (PS); the high-solubility organic solvent is butyl acetate;
a3: dissolution of the solution
Respectively placing the prepared semiconductor solution and the insulating layer solution on a heating plate, standing and dissolving for 24 hours at 60 ℃;
step 2: preparation of devices
B1: cleaning of substrates
Selecting an insulating substrate, sequentially placing the substrate in deionized water, acetone and alcohol, respectively cleaning for 15 minutes by using an ultrasonic cleaning machine, and then drying by using a nitrogen gun;
b2: preparation of source-drain electrode
Adopts a vacuum thermal evaporation coating technologyUnder vacuum condition (10) -4 Pa) evaporating gold with the thickness of 30nm on a substrate by using a stainless steel mask as a source-drain electrode; wherein the thermal evaporation current is 100-160A, and the speed is 0.01-0.05 nm/s;
b3: preparation of semiconductor thin films
Spreading the prepared semiconductor solution on the upper surface of the substrate by a liquid transfer gun, and spin-coating for 5 seconds at the rotating speed of 500rpm by using a spin coater, and then spin-coating for 40-80 seconds at the rotating speed of 2000 rpm; placing the sample on a heating plate to be heated and annealed at 200 ℃ for 45 minutes in a pure argon environment, wherein the semiconductor layer is coated in a spinning mode in the step; the thickness range of the prepared semiconductor film is 35 to 45nm, and the semiconductor film is an active layer.
B4: preparation of insulating layer film
Spreading the prepared insulating layer solution on the upper surface of the semiconductor film by a liquid transfer gun, and homogenizing for 5 seconds at the rotating speed of 500rpm and then 60 seconds at the rotating speed of 2000rpm by a spin coater; in the pure argon environment, the sample which is coated with the insulating layer in the step in a spinning way is placed on a heating plate and is heated and annealed for 2 hours at the temperature of 80 ℃;
b5: preparation of grid electrode
And (3) by calibrating an optical microscope, enabling the opening position of the stainless steel mask plate to correspond to a channel between the source electrode and the drain electrode, and preparing aluminum with the thickness of 60nm on the upper surface of the insulating layer by utilizing a vacuum thermal evaporation coating technology to serve as a gate electrode to obtain the traditional P-type organic thin film transistor.
As shown in fig. 1, fig. 1 is a schematic cross-sectional structure of a conventional P-type organic thin film transistor manufactured according to a comparative example.
Examples
A1: preparation of semiconductor solution
Preparing a P-type organic semiconductor material and an organic solvent according to the mass-to-volume ratio of 8 mg/ml; wherein the P-type organic semiconductor material is: a polymer of 1, 4-dioxodipyrrole and thiophene, DPPT-TT; the organic solvent is p-dichlorobenzene;
a2: preparation of insulating layer solution
Preparing an insulating layer material and a high-solubility organic solvent according to a mass-volume ratio of 80 mg/ml; wherein the insulating layer material is Polystyrene (PS); the high-solubility organic solvent is butyl acetate;
a3: dissolution of the solution
Respectively placing the prepared semiconductor solution and the insulating layer solution on a heating plate, standing and dissolving for 24 hours at 60 ℃;
and 2, step: preparation of devices
B1: cleaning of substrates
Selecting an insulating substrate, sequentially placing the substrate in deionized water, acetone and alcohol, respectively cleaning for 15 minutes by using an ultrasonic cleaning machine, and then drying by using a nitrogen gun;
b2: preparation of source drain electrode
The vacuum thermal evaporation coating technology is adopted, gold particles are placed on a No. 1 thermal evaporation boat, and a mechanical pump and a molecular pump are used for pumping a thermal evaporation cavity to be vacuum of 4.5 multiplied by 10 -4 Under the condition of Pa, gold with the thickness of 30nm is evaporated on the substrate by using a stainless steel mask as a source drain electrode; wherein the thermal evaporation current is 120A, and the rate is 0.02nm/s;
b3: preparation of contact doping layer
Adopting vacuum thermal evaporation coating technology, spreading molybdenum trioxide crystal powder on No. 2 thermal evaporation boat, pumping into vacuum 4.5 × 10 by using mechanical pump and molecular pump -4 A stainless steel mask is utilized to evaporate molybdenum trioxide with the thickness of 3nm on the surface of the source and drain electrodes at the same position as a contact doping layer under the Pa condition, and when the thickness of the molybdenum trioxide is very thin (<1 nm) and the contact doping layer is a discontinuous thin film, which can result in poor device performance when the thickness of the contact doping layer is too high (b:)>6 nm), the low conductivity and bulk resistance of the material itself become gradually apparent, which also results in the performance degradation of the device; wherein the thermal evaporation current is 75A, and the speed is 0.01 nm/s;
b4: preparation of semiconductor thin films
Spreading the prepared semiconductor solution on the upper surface of the substrate through a liquid transfer gun, and spin-coating for 5 seconds at the rotating speed of 500rpm by using a spin coater and then for 60 seconds at the rotating speed of 2000 rpm; placing the sample on a heating plate to be heated and annealed at 200 ℃ for 45 minutes in a pure argon environment, wherein the semiconductor layer is coated in a spinning mode in the step; the thickness range of the prepared semiconductor film is 35-45nm, and the semiconductor film is the active layer.
B5: preparation of insulating layer film
Spreading the prepared insulating layer solution on the upper surface of the semiconductor film by a liquid transfer gun, and homogenizing for 5 seconds at the rotating speed of 500rpm and then 60 seconds at the rotating speed of 2000rpm by a spin coater; placing the sample with the insulating layer coated in a spinning mode in the step on a heating plate in a pure argon environment, and heating and annealing the sample for 2 hours at the temperature of 80 ℃;
b6: preparation of grid electrode
And (3) by calibrating an optical microscope, enabling the opening position of the stainless steel mask plate to correspond to a channel between the source electrode and the drain electrode, and preparing aluminum with the thickness of 60nm on the upper surface of the insulating layer by utilizing a vacuum thermal evaporation coating technology to serve as a gate electrode to obtain the molybdenum trioxide contact doped P-type organic thin film transistor.
As shown in fig. 2, fig. 2 is a schematic cross-sectional structure diagram of a molybdenum trioxide contact doped P-type organic thin film transistor prepared in this embodiment;
FIG. 3 is a graph comparing the transfer characteristics in the saturation region of the organic thin film transistors obtained in the comparative example and the example. Referring to fig. 3, the saturation region transfer characteristic curve of the molybdenum trioxide contact doped transistor prepared by the embodiment is greatly improved. To account for the changes in the specific electrical parameters, table 1 lists the electrical parameters of the switching ratio, mobility, sub-threshold swing, and threshold voltage of the two devices. For the P-type organic thin film transistor of the comparative example, the switching ratio was 10 4 Mobility of 0.144 square centimeters per volt-second, subthreshold swing of the order of 5.69 volts per unit, and threshold voltage of 9.17 volts, whereas for the P-type organic thin film transistor of the present example, the on-off ratio was 3 × 10 5 The mobility was 0.619 square centimeters/(volt · s), the subthreshold swing was 1.56 volts/unit order of magnitude, and the threshold voltage was 4.63 volts. Therefore, the indexes of the four core electrical parameters of the transistor can be observed, and the P-type organic thin film transistor prepared by the inventionThe electrical properties are remarkably improved, and the method has very important significance for further development of the P-type organic thin film transistor.
The contact regulation effect of the molybdenum trioxide contact doped layer on the source/drain electrode and the P-type semiconductor active layer and the hole-promoted injection effect on the P-type organic semiconductor are main reasons for promoting the optimization of the transistor performance. The contact between the semiconductor and the metal electrode in the P-type organic thin film transistor without the interlayer is usually a schottky contact, and such non-ohmic contact generates a large contact resistance, thereby degrading the electrical properties of the thin film transistor. The electrode surface work function of the P-type organic thin film transistor doped by the method is close to the HOMO energy level of the P-type organic semiconductor, so that the Schottky barrier between a source electrode and a drain electrode and the semiconductor is reduced, and the hole transmission is facilitated; and the molybdenum trioxide has the effect of hole doping injection on the semiconductor, so that the capture process of electron holes is influenced, the contact type recombination of electrons and holes is effectively reduced, the carrier concentration of the P-type organic semiconductor film is increased, and the electrical property of the P-type organic thin film transistor is remarkably improved. Referring to Table 1, 3nm molybdenum trioxide (MoO) using gold as a source-drain electrode prepared by the present invention 3 ) Compared with a transistor switch which is prepared by a traditional method and has the advantages that the transistor switch which is used as a contact doping layer, a polymer of 1, 4-dioxodipyrrole and thiophene, namely DPPT-TT, is used as an active layer, polystyrene (PS) is used as an insulating layer and aluminum is used as a gate electrode is 30 times higher than that of a device prepared by the traditional method, the carrier mobility is improved to be 4 times higher than that of the traditional device, and the subthreshold swing and the threshold voltage are obviously reduced.
Therefore, the preparation method can solve the problem of low carrier field effect mobility in the P-type organic thin film transistor, greatly improve various electrical properties of the P-type organic thin film transistor, and has very profound significance for realizing large-scale commercial application of the organic thin film transistor.
TABLE 1
Figure DEST_PATH_IMAGE002

Claims (2)

1. A preparation method of a P-type organic thin film transistor based on molybdenum trioxide contact doping is characterized by comprising the following specific steps:
step 1: preparation of the solution
A1: preparation of semiconductor solution
Preparing a P-type organic semiconductor material and an organic solvent according to the mass-to-volume ratio of 8 mg/ml; wherein the P-type organic semiconductor material is: a polymer of 1, 4-dioxodipyrrole and thiophene, DPPT-TT; the organic solvent is chlorobenzene or p-dichlorobenzene;
a2: preparation of insulating layer solution
Preparing an insulating layer material and a high-solubility organic solvent according to the mass-volume ratio of 80 mg/ml; the insulating layer is made of high-molecular polymer, and the high-solubility organic solvent is acetic acid or butyl acetate;
a3: dissolution of the solution
Respectively placing the prepared semiconductor solution and the insulating layer solution on a heating plate, standing and dissolving for 24 hours at 60 ℃;
and 2, step: preparation of devices
B1: cleaning of substrates
Selecting an insulating substrate, sequentially placing the substrate in deionized water, acetone and alcohol, respectively cleaning for 15 minutes by using an ultrasonic cleaning machine, and then drying by using a nitrogen gun;
b2: preparation of source-drain electrode
The vacuum thermal evaporation coating technology is adopted, gold particles are placed on a first thermal evaporation boat, and a mechanical pump and a molecular pump are used for pumping the vacuum 10 in a thermal evaporation cavity -5 ~10 -4 Under the condition of Pa, gold with the thickness of 30nm is evaporated on the substrate by using a stainless steel mask as a source drain electrode; wherein the thermal evaporation current is 100-160A, and the speed is 0.01-0.05 nm/s;
b3: preparation of contact doped layer
Spreading molybdenum trioxide crystal powder on a second thermal evaporation boat by adopting a vacuum thermal evaporation coating technology, and pumping the thermal evaporation chamber to vacuum 10 by using a mechanical pump and a molecular pump -5 ~10 -4 Under the condition of Pa, evaporating and plating molybdenum trioxide with the thickness of 2-5nm on the surface of the source and drain electrodes at the same position by using a stainless steel mask as a contact doping layer; wherein, the thermal evaporation current is 60-75A, and the speed is 0.01-0.02 nm/s;
b4: preparation of semiconductor thin films
Spreading the prepared semiconductor solution on the upper surface of the substrate by a liquid transfer gun, and homogenizing for 5 seconds at the rotating speed of 500rpm by using a spin coater and then for 40-80 seconds at the rotating speed of 2000 rpm; placing the sample coated with the semiconductor layer in a spinning mode on a heating plate under the pure argon environment, and heating and annealing for 45 minutes at 200 ℃; the thickness range of the prepared semiconductor film is 35 to 45nm, and the semiconductor film is an active layer;
b5: preparation of insulating layer film
Spreading the prepared insulating layer solution on the upper surface of the semiconductor film by a liquid transfer gun, and homogenizing for 5 seconds at the rotating speed of 500rpm and then 60 seconds at the rotating speed of 2000rpm by a spin coater; placing the sample coated with the insulating layer on a heating plate in a pure argon environment, and heating and annealing the sample at 80 ℃ for 2 hours;
b6: preparation of grid electrode
Through the calibration of an optical microscope, enabling the opening position of a stainless steel mask plate to correspond to a channel between a source electrode and a drain electrode, and preparing aluminum with the thickness of 60nm on the upper surface of an insulating layer by utilizing a vacuum thermal evaporation coating technology to serve as a gate electrode to obtain the molybdenum trioxide contact doped P-type organic thin film transistor; wherein:
in the step A2, the high molecular polymer is polystyrene and has a contact angle of at least 90 degrees with water;
in the step B1, the insulating substrate is glass, silicon dioxide or poly terephthalic acid plastic;
the switch ratio of the prepared molybdenum trioxide contact doped P-type organic thin film transistor is 3 multiplied by 10 5 The mobility of the material is 0.619 cm 2 A/volt-sec subthreshold swing of the order of 1.56 volts per unit and a threshold voltage of 4.63 volts.
2. A P-type organic thin film transistor based on molybdenum trioxide contact doping made by the method of claim 1.
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