Apparatus and process for annealing organic semiconductor thin films

Abstract

The application discloses a high-speed annealing equipment and method for an organic semiconductor thin film, and relates to the technical field of the organic semiconductor thin film. The high-speed annealing equipment for the organic semiconductor thin film comprises a sealed cavity for annealing the organic semiconductor thin film, a heating plate arranged in the sealed cavity, a temperature measuring element arranged on the surface of the heating plate and located below the thin film, a liquid nitrogen nozzle connected with the inner wall of the top of the sealed cavity and located directly above the thin film, a power supply electrically connected with the heating plate, and a PID controller electrically connected with the heating plate, the temperature measuring element and the power supply. The application solves the problem that the current thermal annealing method is difficult to realize high-speed and accurate temperature control, and the annealing equipment and method for the organic semiconductor thin film are not mature.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic semiconductor thin film, and particularly relates to an annealing device and process for organic semiconductor thin film. BACKGROUND

[0002] In recent years, organic flexible semiconductor materials have attracted extensive attention. By constructing new conjugated skeletons, the materials have carrier mobilities close to or even exceeding those of amorphous silicon, and the design of side chains improves the solubility and flexibility of the materials. However, the preparation of organic semiconductor thin film usually uses suspension coating or deposition method. The thin film obtained in this way is usually in a thermodynamic non-equilibrium state, and usually generates locally oriented paracrystalline regions and various amorphous regions with glass transition behavior. The complex chain relaxation and crystallization behavior under nano-confinement state significantly affect the electrical and mechanical properties of the materials, which makes the production of organic semiconductor thin film encounter many difficulties, the manufacturing process is complex and immature, the reliability is much lower than that of traditional inorganic materials, and it is still difficult to be commercialized on a large scale.

[0003] Fast heat treatment and precise temperature annealing process can greatly improve the crystallization orientation of organic semiconductor thin film and the relaxation behavior of molecular chains in amorphous regions. However, the current thermal annealing process is difficult to achieve high-speed and precise temperature control, which makes the annealing device and process for organic semiconductor thin film not mature. In view of the above problems, no effective solution has been proposed so far. SUMMARY

[0004] The present application provides an annealing device and process for organic semiconductor thin film to solve the above problems existing in the prior art.

[0005] Technical scheme: an annealing device and process for organic semiconductor thin film, comprising: a sealed cavity for annealing of organic semiconductor thin film; a heating plate arranged in the sealed cavity; a temperature measuring element arranged on the surface of the heating plate and located below the thin film; a liquid nitrogen nozzle connected with the inner wall of the top of the sealed cavity and located directly above the thin film; a power supply electrically connected with the heating plate; and a PID controller electrically connected with the heating plate, the temperature measuring element and the power supply; the temperature measuring element measures the temperature signal of the thin film and converts the temperature signal into an electrical signal which is fed back to the PID controller, and the PID controller sends a control signal to control the power supply and act on the heating plate to heat, so as to accurately control the temperature and anneal the thin film.

[0006] Preferably, the thickness of the heating plate is 1 mm to 10 mm.

[0007] Preferably, the temperature measuring element uses platinum resistance, but is not limited to this.

[0008] As preferred, the liquid nitrogen nozzle is 0.5mm to 5mm away from the heating plate.

[0009] As preferred, the power source adopts current pulse power source, including but not limited to.

[0010] As preferred, the power range of the current pulse power source is 50w to 2000w.

[0011] As preferred, the heating plate has a containing groove, and the temperature measuring element is placed in the containing groove.

[0012] To achieve the above-mentioned purposes, the application provides an annealing process of an organic semiconductor thin film, including the following steps: S1, placing a sample thin film together with a substrate on a heating plate under the protection of an inert gas; S2, providing a power range of 700w to 1200w by a current pulse power source; S3, adjusting the power by a PID controller, heating the heating plate with a thickness range of 5mm to 8mm in a closed cavity, and the heating speed range is 800K / s to 1000K / s; S4, real-time temperature measurement by a temperature measuring element, when the temperature range reaches 300℃ to 380℃, rapidly spraying a cooling source from a liquid nitrogen nozzle at a flow rate of 30ml / min to 50ml / min to cool down, and the cooling speed range is 500K / s to 700K / s; S5, when the temperature range is-70℃ to-50℃, rapidly applying power to the heating plate again to heat it to 150℃ to 180℃ at a speed of 500K / s to 700K / s and keep it for 15min to 30min for annealing treatment; S6, after the annealing is completed, spraying a cooling source from a liquid nitrogen nozzle 5 at a flow rate of 5ml / min to cool down, and after reaching room temperature, the closed cavity can be opened to take out the sample.

[0013] As preferred, the flow rate of the liquid nitrogen nozzle is 10ml / min to 200ml / min.

[0014] As preferred, the heating or cooling speed range is 1K / s to 1000K / s, and the temperature range is-150℃ to 350℃.

[0015] Beneficial effects: In the embodiment of the application, the PID controller is used to accurately control the annealing temperature, the temperature signal of the thin film is measured by the temperature measuring element and converted into an electric signal which is fed back to the PID controller, the PID controller sends control signals to control the power source and the heating plate according to the feedback electric signal, so as to accurately control the temperature and anneal the thin film placed on the substrate, and the purpose of accurate temperature control and annealing is achieved, thereby realizing the technical effect of improving the performance of the thin film, and further solving the technical problem that the current thermal annealing process is difficult to achieve high-speed and accurate temperature control, which makes the annealing equipment and process for the organic semiconductor thin film not mature. BRIEF DESCRIPTION OF DRAWINGS

[0016] Figure 1 is a schematic diagram of the annealing equipment structure of the organic semiconductor thin film of the present application;

[0017] Figure 2 is a schematic diagram of the annealing process of the organic semiconductor thin film of the present application.

[0018] The reference signs are: 1, power supply; 2, PID controller; 3, sealed cavity; 4, heating plate; 5, liquid nitrogen nozzle; 6, thin film; 7, temperature measuring element. DETAILED DESCRIPTION

[0019] In order to enable the personnel in the technical field to better understand the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by the personnel in the field without making creative efforts should belong to the scope of protection of the present application.

[0020] It should be noted that the terms "first", "second" and the like in the specification and claims of the present application and the above-described drawings are used to distinguish similar objects, and do not necessarily indicate a specific order or a chronological sequence. It should be understood that the data thus used can be interchanged under appropriate circumstances, so that the embodiments of the present application described herein can be implemented. In addition, the terms "include" and "have" and any variations thereof are intended to cover non-exclusive inclusion, for example, a process, method, system, product or device that includes a series of steps or units does not necessarily have to be limited to those steps or units clearly listed, but can include other steps or units not clearly listed or inherent to the process, method, product or device.

[0021] In addition, the terms "mount", "set", "provided with", "connect", "connected", "sleeved" should be broadly understood. For example, it can be fixedly connected, detachably connected, or integrally configured; it can be mechanically connected, or electrically connected; it can be directly connected, or indirectly connected through an intermediate medium, or the internal communication between two devices, elements or components. For the personnel in the field, the specific meaning of the above terms in the present application can be understood according to the specific circumstances.

[0022] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to the drawings and in combination with the embodiments.

[0023] As Figure 1As shown, the present application relates to an annealing device and process for organic semiconductor thin film. The annealing device for organic semiconductor thin film comprises: a sealed cavity 3 for annealing organic semiconductor thin film and isolating air; the sealed cavity 3 refers to a cavity with sealing function, which can realize the effect of accommodating other components, thereby providing a place for annealing organic semiconductor thin film and isolating air. A heating plate 4 is arranged in the sealed cavity 3; the heating plate 4 refers to a plate with heating function, which can realize the effect of placing and heating the thin film. At the same time, placing the heating plate 4 in the sealed cavity 3 can ensure that the heating plate 4 is in a good working environment. The bottom of the heating plate 4 can be connected with the sealed cavity by a supporting rod or a supporting plate, which can realize the effect of good fixing and supporting of the heating plate 4. Further, the thickness of the heating plate 4 is 1mm to 10mm. By providing a variety of thicknesses, it can adapt to various use occasions, thereby realizing the effect of zero active use. Preferably, the thickness of the heating plate is 5mm to 8mm, which can realize the effect of good heating effect and structural strength. The thin film 6 on the substrate is arranged on the heating plate 4; by arranging the thin film 6 on the substrate, a good fixing effect can be realized, thereby realizing the effect of facilitating subsequent processing.

[0024] The temperature measuring element 7 is arranged on the surface of the heating plate 4 and below the substrate; by arranging the temperature measuring element 7 on the surface of the heating plate 4, a good fixing effect can be realized; at the same time, it can also realize the effect of accurate temperature detection, thereby realizing the effect of good temperature feedback. Further, the number of temperature measuring elements 7 can be multiple. It can realize the effect of improving the temperature measurement accuracy, thereby avoiding the situation of false measurement. Preferably, the temperature measuring element 7 is located at the center of the surface of the heating plate 4. It can realize the effect of accurately measuring the temperature of the thin film.

[0025] The liquid nitrogen nozzle 5 is connected with the inner wall of the top of the sealed cavity 3 and located directly above the thin film; the liquid nitrogen nozzle 5 is used to provide a cold source for rapid cooling of the thin film; by connecting the bottom of the liquid nitrogen nozzle 5 with the inner wall of the top of the cavity, a good fixing and supporting effect of the liquid nitrogen nozzle 5 can be realized, and by directing the nozzle to the thin film, a rapid cooling effect of the thin film can be realized, thereby realizing a good annealing effect, and further realizing the effect of improving the performance of the thin film. Further, the distance between the liquid nitrogen nozzle 5 and the heating plate 4 is 0.5mm to 5mm. It can realize the effect of distance adjustment according to the actual use, thereby realizing the effect of good cooling adjustment. Further, the liquid nitrogen nozzle 5 is connected with the inner wall of the top of the sealed cavity 3. The connection mode includes but is not limited to the connection mode of groove and clamping block, which can realize the effect of convenient position adjustment, thereby realizing the effect of zero active use.

[0026] The power supply 1 is electrically connected with the heating plate 4; by electrically connecting the power supply 1 with the heating plate 4, the effect of providing pulse current for high-speed temperature rise of the device can be achieved, thereby achieving good electric heating effect and further achieving the effect of rapid temperature rise of the thin film. Further, the power supply 1 includes but is not limited to: current pulse power supply 1. The control accuracy of the power supply 1 can be improved, thereby achieving good temperature control effect.

[0027] The PID controller 2 is electrically connected with the heating plate 4, the temperature measuring element 7 and the power supply 1 respectively; by electrically connecting the PID controller 2 with the heating plate 4, the temperature measuring element 7 and the power supply 1, good electrical signal transmission effect can be achieved, thereby providing guarantee for accurate control. At the same time, by arranging the PID controller 2, the current intensity of the power supply 1 is controlled to accurately control the temperature in the annealing process.

[0028] The temperature signal of the thin film is measured by the temperature measuring element 7 and converted into an electrical signal and fed back to the PID controller 2; the PID controller 2 sends control signals according to the feedback electrical signal to control the power supply 1 to supply power and act on the heating plate 4 to heat, so as to accurately control the temperature and anneal the thin film 6. By using the temperature measuring element 7 to measure the temperature of the thin film in contact with it, the temperature signal is converted into an electrical signal and fed back to the PID controller 2; the PID controller 2 sends control signals according to the feedback electrical signal to control the heating plate 4 and the power supply 1 to act, thereby realizing accurate regulation and control of the crystallinity and thermal relaxation behavior of the organic semiconductor thin film, and further improving the carrier mobility, tensile strength and flexibility of the thin film. The structure of the crystalline and amorphous regions of the organic semiconductor thin film obtained by spin coating or deposition can be greatly improved, thereby improving the overall electrical and mechanical properties of the thin film.

[0029] From the above description, it can be seen that the present application achieves the following technical effects:

[0030] In the embodiment of the present application, the PID controller 2 is used to accurately control the annealing temperature; the temperature signal of the thin film is measured by the temperature measuring element 7 and converted into an electrical signal and fed back to the PID controller 2; the PID controller 2 sends control signals according to the feedback electrical signal to control the power supply 1 and the heating plate 4 to act, so as to accurately control the temperature and anneal the thin film 6 placed on the substrate, thereby achieving the purpose of accurate temperature control and annealing, realizing the technical effect of improving the performance of the thin film, and further solving the technical problem that the current thermal annealing process cannot achieve high-speed and accurate temperature control, which makes the annealing equipment and process for organic semiconductor thin film not mature.

[0031] Further, the temperature measuring element 7 includes but is not limited to: platinum resistance. Good temperature measurement effect can be achieved, thereby improving the accuracy of temperature acquisition and feedback.

[0032] Furthermore, the heating plate 4 has a receiving groove in which the temperature measuring element 7 is placed. This allows for effective placement of the temperature measuring element 7, achieving both good placement and temperature measurement while also providing good heating performance.

[0033] like Figure 2 As shown, in terms of process, this invention also provides an annealing process for organic semiconductor thin films, including the following steps: S1, placing the sample thin film on a heating plate under the protection of an inert gas; S2, providing power in the range of 700W to 1200W through a current pulse power supply; S3, adjusting the power through a PID controller to heat the heating plate located in a sealed cavity, with a heating rate range of 800K / s to 1000K / s; S4, using a temperature sensing element to perform real-time temperature measurement, and rapidly reducing the temperature at a rate of 30ml / min after the temperature reaches 300℃ to 380℃. Cooling is achieved by injecting a cold source from the liquid nitrogen nozzle at a flow rate of 50 ml / min to 50 ml / min, with a cooling rate range of 500 K / s to 700 K / s; S5, once the temperature reaches -70℃ to -50℃, power is rapidly applied to the heating plate to raise the temperature again to 150℃ to 180℃ at a rate of 500 K / s to 700 K / s and maintain it for 15 min to 30 min for annealing; S6, after annealing, cooling is achieved by injecting a cold source from the liquid nitrogen nozzle 5 at a flow rate of 5 ml / min. Once room temperature is reached, the sealed cavity can be opened to remove the sample.

[0034] Example 1

[0035] This embodiment provides an annealing process for organic semiconductor thin films, specifically including:

[0036] The sample film and substrate are placed together on the heating plate 4. A current pulse power supply 1 provides 1000W of power, and the power is regulated by the PID controller 2 to heat the 5 mm thick heating plate 4 located in the sealed cavity 3 at a heating rate of 1000 K / s. The platinum resistance temperature measuring element 7 measures the temperature in real time. After the temperature reaches 350℃, the cold source is quickly sprayed from the liquid nitrogen nozzle 5 at a flow rate of 50 ml / min to cool it down at a cooling rate of 700 K / s. After the temperature reaches -50℃, the power is quickly applied to the heating plate again to heat it up to 180℃ at a rate of 500 K / s and held for 15 min for annealing. After annealing, the cold source is sprayed from the liquid nitrogen nozzle 5 at a flow rate of 5 ml / min to cool it down. After the temperature reaches room temperature, the sealed cavity can be opened and the sample can be taken out.

[0037] Example 2

[0038] This embodiment provides an annealing process for organic semiconductor thin films, specifically including:

[0039] The sample film and the substrate are placed on the hot plate 4, the current pulse power supply 1 provides 800W power, the PID controller 2 adjusts the power, the 5mm-thick hot plate 4 in the closed cavity 3 is heated, the heating rate is 900K / s, the platinum resistance temperature measuring element 7 measures the temperature in real time, after the temperature reaches 300℃, the cooling source is sprayed by the liquid nitrogen nozzle 5 at a flow rate of 40ml / min, the cooling rate is 600K / s, after the temperature reaches-50℃, the power is applied to the hot plate again to heat it to 160℃ at a rate of 500K / s and keep it for 25min for annealing treatment, after the annealing is completed, the cooling source is sprayed by the liquid nitrogen nozzle 5 at a flow rate of 5ml / min, and the sample can be taken out after the closed cavity is opened when the temperature reaches room temperature.

[0040] Example 3

[0041] The embodiment provides an annealing process of an organic semiconductor thin film, and specifically comprises the following steps:

[0042] The sample film and the substrate are placed on the hot plate 4, the current pulse power supply 1 provides 1200W power, the PID controller 2 adjusts the power, the 5mm-thick hot plate 4 in the closed cavity 3 is heated, the heating rate is 1000K / s, the platinum resistance temperature measuring element 7 measures the temperature in real time, after the temperature reaches 380℃, the cooling source is sprayed by the liquid nitrogen nozzle 5 at a flow rate of 50ml / min, the cooling rate is 500K / s, after the temperature reaches-70℃, the power is applied to the hot plate again to heat it to 160℃ at a rate of 700K / s and keep it for 20min for annealing treatment, after the annealing is completed, the cooling source is sprayed by the liquid nitrogen nozzle 5 at a flow rate of 5ml / min, and the sample can be taken out after the closed cavity is opened when the temperature reaches room temperature.

[0043] Example 4

[0044] The embodiment provides an annealing process of an organic semiconductor thin film, and specifically comprises the following steps:

[0045] The sample film is placed on the heating plate 4 together with the substrate, the power of 700W is provided by the current pulse power supply 1, the power is adjusted by the PID controller 2, the heating plate 4 with a thickness of 8mm in the closed cavity 3 is heated, the heating speed is 800K / s, the platinum resistance temperature measuring element 7 is used for real-time temperature measurement, after the temperature reaches 300 DEG C, the cooling source is sprayed by the liquid nitrogen nozzle 5 at a flow rate of 30ml / min, the cooling speed is 500K / s, after the temperature reaches-40 DEG C, the power is applied to the heating plate again to heat it to 150 DEG C at a speed of 600K / s and keep for 30min to perform annealing treatment, after the annealing is finished, the cooling source is sprayed by the liquid nitrogen nozzle 5 at a flow rate of 5ml / min, and the sample can be taken out after the temperature reaches room temperature.

[0046] Further, the inert gas includes but is not limited to: helium, nitrogen or argon. The effect of various gas selection can be realized; at the same time, the film can be in a good environment, so as to realize the good heating or cooling effect.

[0047] Further, the flow rate of the liquid nitrogen nozzle is 10ml / min to 200ml / min. The effect of a wide range of flow rate selection can be realized, so as to realize the effect of flow rate setting according to the actual use occasion.

[0048] Further, the temperature range is-150 DEG C to 350 DEG C. The effect of temperature selection can be provided, so as to realize the effect of rapid heating or cooling; at the same time, high temperature or low temperature can be provided, so as to realize the effect on the film.

[0049] The application also has the following beneficial effects:

[0050] 1. The high-speed heating and cooling of up to 1000K / s can be realized, so that the organic semiconductor film can be rapidly cooled from the molten state to below the glass transition temperature, and then annealed at a specific temperature.

[0051] 2. The local defects of the organic semiconductor film are greatly reduced in the high-temperature and annealing process by the protection of the inert gas atmosphere and the rapid temperature control.

[0052] The preferred embodiments of the application are described in detail above with reference to the drawings, but the application is not limited to the specific details in the above-described embodiments, and various equivalent transformations can be made to the technical solutions of the application within the technical concept of the application, and these equivalent transformations all belong to the protection scope of the application.

Claims

1. An annealing apparatus for organic semiconductor thin films, characterized in that, The application relates to an organic semiconductor thin film annealing device, which comprises the following parts: a sealed cavity for organic semiconductor thin film annealing; a heating plate arranged in the sealed cavity; a temperature measuring element arranged on the surface of the heating plate and located below the thin film; a liquid nitrogen nozzle connected with the inner wall of the top of the sealed cavity and located directly above the thin film; a power supply electrically connected with the heating plate; and a PID controller electrically connected with the heating plate, the temperature measuring element and the power supply; the temperature signal of the thin film is measured by the temperature measuring element and converted into an electric signal which is fed back to the PID controller; the PID controller sends a control signal to control the power supply and act on the heating plate for heating according to the feedback electric signal, so that the thin film is accurately temperature-controlled and annealed. The thickness of the heating plate is 1mm to 10mm. The temperature measuring element is a platinum resistance.

2. The apparatus for annealing an organic semiconductor thin film according to claim 1, wherein The distance between the liquid nitrogen nozzle and the heating plate is 0.5mm to 5mm.

3. The apparatus for annealing an organic semiconductor thin film according to claim 1, wherein The power supply is a current pulse power supply.

4. The apparatus for annealing an organic semiconductor thin film according to claim 1, wherein The power interval of the current pulse power supply is 50w to 2000w.

5. The apparatus for annealing an organic semiconductor thin film according to claim 1, wherein The heating plate has a containing groove, and the temperature measuring element is placed in the containing groove.

6. The apparatus for annealing an organic semiconductor thin film according to claim 5, wherein The application further discloses a method for annealing an organic semiconductor thin film, which comprises the following steps:

7. The apparatus according to claim 1, wherein S1, placing a sample thin film on the heating plate under the protection of inert gas; S2, providing power with an interval of 700w to 1200w by the current pulse power supply; S3, adjusting the power by the PID controller to heat the heating plate in the sealed cavity, and the heating speed interval is 800K / s to 1000K / s; S4, real-time temperature measurement is conducted by the temperature measuring element, when the temperature interval reaches 300 DEG C to 380 DEG C, the cooling source is sprayed by the liquid nitrogen nozzle at a flow rate of 30ml / min to 50ml / min to rapidly cool, and the cooling speed interval is 500K / s to 700K / s; S5, when the temperature interval is-70 DEG C to-50 DEG C, the power is rapidly applied to the heating plate again to heat it at a speed of 500K / s to 700K / s to 150 DEG C to 180 DEG C and keep for 15min to 30min for annealing treatment; S6, after the annealing is completed, the cooling source is sprayed by the liquid nitrogen nozzle at a flow rate of 5ml / min to cool, and after the room temperature is reached, the sealed cavity is opened to take out the sample.

8. An annealing process of an organic semiconductor thin film, characterized by, The flow rate of the liquid nitrogen nozzle is 10ml / min to 200ml / min. The heating or cooling speed interval is 1K / s to 1000K / s, and the temperature range is-150 DEG C to 350 DEG C.

9. The annealing process of an organic semiconductor thin film according to claim 8, wherein ​ 10. The annealing process of an organic semiconductor thin film according to claim 8, wherein ​

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