Organic molecule semiconductor device growth system and method based on vacuum interconnection

Abstract

The invention discloses an organic molecule semiconductor device growth system and method based on vacuum interconnection, the growth system comprises a transfer cavity with an ultrahigh vacuum environment and a plurality of functional cavities with controllable heating devices, and each functional cavity is used for accommodating a plurality of growth sources; the vacuum device is communicated to the transfer cavity and / or the functional cavity; and the mechanical arm is at least used for transferring the sample table containing the substrate from the transfer cavity to the target functional cavity so as to deposit a layer structure of a corresponding material in a working state. By optimizing the growth technology of the multi-structure organic molecule semiconductor device, the growth controllability is effectively improved, and cross contamination is avoided, so that the quality controllability is improved.

Description

Technical Field

[0001] The invention belongs to the field of semiconductor technology, and in particular relates to a vacuum interconnection-based organic molecular semiconductor device growth system and method. Background Art

[0002] Organic thin film optoelectronic devices based on organic semiconductor materials, including organic electroluminescence (OLED), organic thin film photovoltaic (OPV), organic thin film transistor (OFET), etc., have made great progress in performance parameters such as photoelectric conversion efficiency and semiconductor mobility in recent years. The quantum luminescence efficiency of OLED has reached more than 25%, the photoelectric conversion efficiency of OPV has reached more than 17%, and the carrier mobility in OFET has reached 15cm 2 / (V·s), showing extremely broad application prospects in the fields of solar cells, displays, flexible wearable devices, etc. But overall, there is still a certain gap between the efficiency performance of organic molecular semiconductor devices and traditional inorganic semiconductor devices. More importantly, organic molecular semiconductor devices usually show relatively rapid performance decay, and their reliability is still far from practical. Among them, the performance between molecular semiconductor materials and functional film interfaces is the key to affecting the performance and reliability of organic molecular semiconductor devices, and has become an important topic in the research of organic molecular semiconductor optoelectronic devices.

[0003] The control of the surface morphology and molecular arrangement of functional materials in semiconductor devices has a huge impact on the performance of the device. For the preparation and research of printed electronic devices, the molecular arrangement of each functional layer material and the surface and interface control of each layer of functional materials are also critical to the performance research of printed devices. Thermal evaporation is currently the main method for vacuum preparation of organic optoelectronic devices. Unlike the atomic-level deposition rate of MBE thin films, thermal evaporation coating equipment is faster and can reach the nanometer level. It also has an effective and controllable thin film deposition process. However, the vacuum degree of ordinary thermal evaporation coating equipment is usually 10 -4 ~10 -5 Pa, impurities in the background vacuum will participate in the growth and affect the quality of the film, especially water molecules and oxygen can easily oxidize free radical anions, directly affecting the performance of n-type semiconductor materials.

[0004] Therefore, in view of the above technical problems, it is necessary to provide a vacuum interconnection-based organic molecular semiconductor device growth system and method.

[0005] The information disclosed in this background technology section is only intended to enhance the understanding of the overall background of the invention and should not be regarded as an acknowledgment or any form of suggestion that the information constitutes the prior art already known to a person skilled in the art. Summary of the invention

[0006] The object of the present invention is to provide a vacuum interconnection-based organic molecular semiconductor device growth system and method.

[0007] In order to achieve the above object, a technical solution provided by a specific embodiment of the present invention is as follows:

[0008] Organic molecular semiconductor device growth system based on vacuum interconnection, including

[0009] A transfer chamber with an ultra-high vacuum environment and a plurality of functional chambers with controllable heating devices, each of the functional chambers being used to accommodate a plurality of growth sources;

[0010] A vacuum device connected to the transfer chamber and / or the functional chamber;

[0011] The robot arm is at least used to transfer the sample stage containing the substrate from the transfer chamber to the target functional chamber to deposit a layer structure of a corresponding material in a working state.

[0012] In one or more embodiments of the present invention, the functional cavity is selected from an organic growth cavity, a metal growth cavity, and an oxide growth cavity.

[0013] In one or more embodiments of the present invention, the organic growth chamber is used to carry an organic small molecule semiconductor material as a growth source.

[0014] In one or more embodiments of the present invention, the organic small molecule semiconductor material is selected from p-type semiconductor materials (such as NPB, TAPC), p-type doped semiconductor materials (such as MoO 3 , HAT-CN), n-type semiconductor materials (such as Alq3, TPBi, BPhen), n-type doped semiconductor materials (such as C 60 ,CsCO 3 ).

[0015] In one or more embodiments of the present invention, the temperature range of the controllable heating device of the functional chamber is no higher than 1500°C.

[0016] In one or more embodiments of the present invention, during operation, the sample stage is further connected to a rotating device to drive the substrate to rotate within a plane where the sample stage supporting surface is located.

[0017] In one or more embodiments of the present invention, a film thickness meter is also provided in the functional chamber to monitor the thickness of the current film.

[0018] In one or more embodiments of the present invention, the vacuum device is selected from an ion pump and a titanium sublimation pump.

[0019] In one or more embodiments of the present invention, a cooling system is further included, wherein the cooling system is used to provide cooling for the vacuum device and / or the film thickness instrument and / or the controllable heating device.

[0020] In one or more embodiments of the present invention, a method for using a vacuum interconnect-based organic molecular semiconductor device growth system includes:

[0021] (1) Manually transfer the substrate to the sample stage of the transfer chamber through a vacuum pipe;

[0022] (2) The sample stage is transferred to a preset point in the selected functional chamber by the manipulator of the transfer chamber, and the corresponding growth source is heated to deposit a film on the substrate, and the temperature is cooled to room temperature after the growth is completed;

[0023] (3) The sample stage is then transferred to the next chamber to grow the next layer of material, and the above growth steps are repeated;

[0024] (4) After all materials have been grown, quasi-in-situ characterization is performed through vacuum interconnection.

[0025] Compared with the prior art, the organic molecular semiconductor device growth system and method based on vacuum interconnection of the present invention has the following advantages:

[0026] (1) Higher vacuum degree in the cavity ensures that the grown organic molecular semiconductor materials are of higher purity and exhibit intrinsic physical and chemical properties, and the accuracy and repeatability of growth control are greatly improved.

[0027] (2) Only one type of organic molecular film can be grown in a single organic growth chamber to prevent cross contamination.

[0028] (3) The comprehensive utilization of multiple cavities realizes the growth of organic matter, oxide dielectric layer and electrons, and the ultra-high vacuum interconnection constitutes a complete organic semiconductor device system, which significantly improves the device construction efficiency.

[0029] (4) The equipment is interconnected by vacuum, and samples can be directly loaded and unloaded from the vacuum pipe. There is no need to restore the entire chamber to atmosphere and then re-evacuate the chamber, which reduces waiting time and gas contamination to the chamber.

[0030] (5) The parameters such as sample transfer position and growth process can be generated into files, and one-click sample transfer and one-click growth can be achieved through calling, with high repeatability. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments recorded in the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0032] Figure 1This is a schematic diagram of the structure of an organic molecular semiconductor device growth system based on vacuum interconnection in one embodiment of the present invention, wherein 1. transfer chamber; 1-1. transfer chamber hollow device; 2. metal growth chamber; 2-1. functional chamber vacuum device; 2-2. film thickness meter; 2-3. control system; 3, 4, 5. organic growth chamber.

[0033] Figure 2 This is a microscopic photograph of a sample according to an embodiment of the present invention.

[0034] Figure 3 This is a microscopic photograph of a sample according to an embodiment of the present invention. DETAILED DESCRIPTION

[0035] In order to enable those skilled in the art to better understand the technical solutions of the present invention, the technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0036] like Figure 1 The vacuum interconnected organic molecule semiconductor device growth system of the present invention is a comprehensive growth device that can quickly complete the preparation of various types of organic small molecule semiconductor materials (including p-type, p-type doped, n-type, and n-type doped) under ultra-high vacuum conditions, and assemble them into device-related dielectric materials (oxides) and electrode materials (metals). Compared with the traditional solution method, the ultra-high vacuum preparation method can more accurately control the deposition process of organic molecules, eliminate the influence of solvent molecules on the film, and is an ideal means for experimental research on molecular semiconductor heterojunction interfaces.

[0037] As an embodiment, the system is mainly composed of 6 ultra-high vacuum chambers, made of stainless steel, and the background vacuum is 10 -8Pa level, which reduces the impurity pollution in the environment to an extremely low level. The 6 chambers include 1 transfer chamber and 5 functional chambers (3 organic growth chambers 3, 4, 5, 1 metal growth chamber 2, and 1 oxide growth chamber 1). The transfer chamber has an ion pump and a titanium sublimation pump to maintain ultra-high vacuum, and an electric-driven manipulator for automatic sample transfer between functional chambers, without the need to restore atmospheric pressure and re-vacuum. More than 10 growth sources are installed in the functional chamber. More than 10 materials can be grown in a single injection, and different types of organic films are grown in different chambers, avoiding material cross-contamination in traditional single-chamber systems. The temperature range of the growth source covers room temperature to 1500 degrees Celsius, meeting the needs of most molecular semiconductor devices. In addition, each functional chamber is equipped with a heating stage and a film thickness meter 2-2 for sample heating and real-time monitoring of film thickness, so as to more accurately control the growth quality and speed of organic thin films, as well as respective dry pumps and molecular pumps for maintaining ultra-high vacuum. The metal growth chamber and oxide growth chamber can also be additionally equipped with ion pumps to enhance the pumping speed, speed up the background vacuum recovery speed after the growth is completed, and shorten the growth interval.

[0038] The automatic control system 2-3 includes digital monitoring and control of the vacuum system (such as the transfer chamber hollow device 1-1 and the functional chamber vacuum device 2-1 as shown in the figure), the sample transfer system, the growth system, the water cooling system, etc. The vacuum system can remotely control the start and stop of the pump group and monitor the vacuum state in the chamber; the sample transfer system can accurately adjust the angle and forward distance of the manipulator and store them in the system to achieve one-key sample transfer; the growth system can independently control the rotation, lifting, extension and retraction of the sample stage, etc., and retain multiple preset points for one-key operation, as well as the temperature control and baffle control of the sample stage and multiple beam sources. It can also program up to 26 growth parameters and arrange them arbitrarily to generate process flows, and achieve one-key growth by saving and calling; the water cooling system includes the regulation of the cooling water and compressed air pressure and flow of each beam source and film thickness instrument. In addition, the system also includes the function of recording historical data of each parameter to facilitate problem tracing.

[0039] This constitutes a complete and comprehensive organic molecular semiconductor film and device preparation platform that can meet the preparation and application of most organic functional films and devices, and is a research tool in the field of molecular semiconductors and devices.

[0040] The sample transfer, growth, heating and other processes involved in this system are all realized through the program control of the independently developed automatic control system. The specific usage is as follows:

[0041] (1) The substrate is manually transferred to the sample parking table of the transfer chamber through the vacuum pipe by using a transfer rod; (2) The transfer chamber robot automatically transfers the sample table to a preset point in the designated functional chamber; (3) One or more growth sources are raised to the target temperature at a certain speed through the control system, and the substrate is heated by a heating table; (4) After reaching the target temperature and stabilizing, the substrate is rotated at a constant speed, the baffle is opened for growth, and the film growth rate and thickness are monitored by a film thickness meter; (5) After the growth is completed, the growth source is cooled to room temperature, and the sample is transferred to the next chamber by a robot to continue growing the next layer of material according to the above steps; (6) After all the materials have been grown, the sample is transferred out by a robot, and further quasi-in-situ characterization can be performed through vacuum interconnection.

[0042] (1) Higher cavity vacuum ensures that the grown organic molecular semiconductor materials are of higher purity and exhibit intrinsic physical and chemical properties, and the accuracy and repeatability of growth control are greatly improved.

[0043] (2) A single organic growth chamber only grows one type of organic molecular film to prevent cross contamination.

[0044] (3) Multi-cavity organic matter growth, oxide dielectric layer growth, and electron growth are interconnected in ultra-high vacuum to form a complete organic semiconductor device system, significantly improving device construction efficiency.

[0045] (4) The equipment is interconnected by vacuum, and samples can be directly loaded and unloaded from the vacuum pipe. There is no need to restore the entire chamber to the atmosphere and then re-evacuate the chamber, which reduces waiting time and gas contamination to the chamber.

[0046] (5) The parameters such as sample transfer position and growth process can be generated into files, and one-click sample transfer and one-click growth can be achieved through calling, with high repeatability.

[0047] Embodiment 1:

[0048] Add 99.9995% pure MoO into the crucible. 3 powder.

[0049] 2 inches Al 2 O 3 The (0001) alumina substrate was heated to 1200°C in pure oxygen for 4 h.

[0050] The processed alumina substrate is transferred into the RDC transfer chamber through a vacuum pipe.

[0051] The RDC transfer chamber manipulator delivers the alumina substrate to the oxide chamber sample stage.

[0052] The sample stage was heated to 800°C and treated under ultra-high vacuum conditions for 1 h.

[0053] The sample stage was cooled to 300°C, and MoO 3 The beam source temperature was raised to 535°C.

[0054] Film thickness meter parameter selection MoO 3 , and move to the predetermined growth position, open the beam source baffle, and measure the growth rate

[0055] Retract the film thickness gauge, move the sample stage to the predetermined growth position, open the sample stage baffle and start growth.

[0056] After timing for 100 minutes, close the sample stage baffle to stop the growth.

[0057] The sample was kept at room temperature for 60 min and cooled to room temperature at a rate of 5 °C / s.

[0058] The RDC robot retrieves the sample and returns it to the vacuum line.

[0059] The thickness was measured by FIB through the vacuum pipe and the thickness was 119.8nm, which is close to the target thickness. Figure 2 shown.

[0060] Embodiment 2:

[0061] Alq3 with a purity of 99% was added into the organic cavity crucible, and Au particles with a purity of 99.999% were added into the metal cavity crucible.

[0062] A 2-inch Al2O3 (0001) aluminum oxide substrate was heated to 1200°C in pure oxygen for 4 hours.

[0063] The processed alumina substrate is transferred into the RDC transfer chamber through a vacuum pipe.

[0064] The RDC transfer chamber manipulator delivers the alumina substrate to the organic chamber sample stage.

[0065] The sample stage was heated to 800°C and treated under ultra-high vacuum conditions for 1 h.

[0066] The sample stage was cooled to 50°C and the Alq3 beam source was heated to 300°C.

[0067] Select Alq3 as the film thickness instrument parameter, move to the predetermined growth position, open the beam source baffle, and measure the growth rate

[0068] Retract the film thickness gauge, move the sample stage to the predetermined growth position, open the sample stage baffle and start growth.

[0069] After timing for 100 minutes, close the sample stage baffle to stop the growth.

[0070] The sample was cooled to room temperature at a rate of 5°C / s.

[0071] The RDC transfer chamber robot retrieves the alumina substrate and sends it to the metal chamber sample stage.

[0072] The sample stage was kept at room temperature and the Au beam source was heated to 1220°C.

[0073] Select Au as the film thickness meter parameter, move to the predetermined growth position, open the beam source baffle, and measure the growth rate

[0074] Retract the film thickness gauge, move the sample stage to the predetermined growth position, open the sample stage baffle and start growth.

[0075] After timing for 40 minutes, close the sample stage baffle to stop the growth.

[0076] The RDC robot retrieves the sample and returns it to the vacuum line.

[0077] The thickness of Alq3 was measured to be 126.8 nm by FIB thickness analysis through the vacuum pipe, which is close to the target thickness. Figure 3 shown.

[0078] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above and that the present invention can be implemented in other specific forms without departing from the spirit or essential features of the present invention. Therefore, the embodiments should be considered exemplary and non-restrictive in all respects, and the scope of the present invention is defined by the appended claims rather than the above description, and it is intended that all changes falling within the meaning and scope of the equivalent elements of the claims be included in the present invention.

[0079] In addition, it should be understood that although the present specification is described according to implementation modes, not every implementation mode contains only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment may also be appropriately combined to form other implementation modes that can be understood by those skilled in the art.

Claims

1. A vacuum interconnection-based organic molecular semiconductor device growth system, comprising: A transfer chamber with an ultra-high vacuum environment and a plurality of functional chambers with controllable heating devices, each of the functional chambers being used to accommodate a plurality of growth sources; A vacuum device connected to the transfer chamber and / or the functional chamber; The robot arm is at least used to transfer the sample stage containing the substrate from the transfer chamber to the target functional chamber to deposit a layer structure of a corresponding material in a working state.

2. The organic molecular semiconductor device growth system based on vacuum interconnection according to claim 1, characterized in that: The functional cavity is selected from an organic growth cavity, a metal growth cavity, and an oxide growth cavity.

3. The organic molecular semiconductor device growth system based on vacuum interconnection according to claim 2, characterized in that: The organic matter growth chamber is used to carry organic small molecule semiconductor materials as growth sources.

4. The organic molecular semiconductor device growth system based on vacuum interconnection according to claim 3, characterized in that: The organic small molecule semiconductor material is selected from p-type semiconductor material, p-type doped semiconductor material, n-type semiconductor material, and n-type doped semiconductor material.

5. The organic molecular semiconductor device growth system based on vacuum interconnection according to claim 1, characterized in that: The temperature range of the controllable heating device of the functional cavity is not higher than 1500°C.

6. The vacuum interconnection-based organic molecular semiconductor device growth system according to claim 1, characterized in that: During operation, the sample stage is also connected to a rotating device to drive the substrate to rotate within the plane where the sample stage supporting surface is located.

7. The organic molecular semiconductor device growth system based on vacuum interconnection according to claim 1, characterized in that: A film thickness meter is also provided in the functional cavity to monitor the thickness of the current film.

8. The organic molecular semiconductor device growth system based on vacuum interconnection according to claim 1, characterized in that: The vacuum device is selected from an ion pump and a titanium sublimation pump.

9. The organic molecular semiconductor device growth system based on vacuum interconnection according to any one of claims 1 to 8, characterized in that: The invention also comprises a cooling system, wherein the cooling system is used for cooling the vacuum device and / or the film thickness instrument and / or the controllable heating device.

10. A method for using the vacuum interconnection-based organic molecular semiconductor device growth system according to any one of claims 1 to 9, characterized in that: include (1) Manually transfer the substrate to the sample stage of the transfer chamber through a vacuum pipe; (2) The sample stage is transferred to a preset point in the selected functional chamber by the manipulator of the transfer chamber, and the corresponding growth source is heated to deposit a film on the substrate, and the temperature is cooled to room temperature after the growth is completed; (3) The sample stage is then transferred to the next chamber to grow the next layer of material, and the above growth steps are repeated; (4) After all materials have been grown, quasi-in-situ characterization is performed through vacuum interconnection.

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