Low-temperature atomic layer deposition equipment and method for heat-sensitive material

Abstract

The invention discloses low-temperature atomic layer deposition equipment and a low-temperature atomic layer deposition method for a heat-sensitive material, relates to the technical field of atomic layer deposition, and aims to solve the problem of low product yield caused by a high-temperature or low-temperature deposition method in the prior art. The equipment at least comprises an atomic layer deposition reaction chamber, a plasma gas reaction chamber, a first gas channel, a second gas channel and a microbalance, the plasma gas reaction chamber is connected with the atomic layer deposition reaction chamber; the microbalance is arranged in the atomic layer deposition reaction chamber and is used for placing a heat-sensitive material and collecting the growth rate of the film thickness on the heat-sensitive material; the first gas channel is connected with the atomic layer deposition reaction chamber and is used for conveying a metal precursor to the atomic layer deposition reaction chamber; the second gas channel is connected with the plasma gas reaction chamber and is used for conveying preset gas to the plasma gas reaction chamber; therefore, the uniform deposition of the low-temperature nanoscale film on the surface of the heat-sensitive material is realized, and the yield of products is improved.

Description

Technical Field

[0001] The present invention relates to the technical field of atomic layer deposition, and in particular to a low-temperature atomic layer deposition device and method for heat-sensitive materials. Background Art

[0002] Atomic Layer Deposition (ALD) is a high-precision thin film deposition technology based on Chemical Vapor Deposition (CVD), which is a technology for depositing material substances layer by layer on the surface of a substrate in the form of a single atomic film based on chemical vapor. Two or more precursor chemicals containing different elements of the material to be deposited are introduced onto the substrate surface one by one, one at a time. Each precursor saturates the surface to form a single layer of material.

[0003] Currently, the atomic layer deposition process includes high-temperature processes and low-temperature processes. The traditional ALD process requires high temperature, that is, the temperature needs to be greater than 200 °C. In this case, it will cause thermal deformation of flexible substrates (PET, PI), and it is not suitable for heat-sensitive substrates such as PET, PI and other heat-sensitive substrates; while in the low-temperature ALD process, there will be problems such as insufficient film density and poor water and oxygen barrier performance of the thin film; both will lead to a decrease in the yield of the product.

[0004] In view of this, in order to avoid the above problems, it is urgent to design a more advanced deposition device and perform corresponding process optimization to solve the problem of low product yield caused by high-temperature or low-temperature deposition methods in the prior art. Summary of the Invention

[0005] The purpose of the present invention is to provide a low-temperature atomic layer deposition device and method for heat-sensitive materials, which can reduce the dissociation temperature of the atomic layer deposition reaction chamber to below 120 degrees Celsius, and can monitor the film thickness growth rate of the oxide thin film, realizing uniform deposition of low-temperature nanoscale thin films on the surface of heat-sensitive materials, improving the product yield, and solving the problem of low product yield caused by high-temperature or low-temperature deposition methods in the prior art.

[0006] In order to achieve the above purpose, the present invention provides the following technical solutions:

[0007] In the first aspect, the present invention provides a low-temperature atomic layer deposition device for heat-sensitive materials, and the device at least includes:

[0008] An atomic layer deposition reaction chamber, a plasma gas reaction chamber, a first gas channel, a second gas channel, and a microbalance;

[0009] The plasma gas reaction chamber is connected to the atomic layer deposition reaction chamber, and the plasma gas reaction chamber is used to generate and transport plasma gas to the atomic layer deposition reaction chamber within a preset time period;

[0010] The microbalance is disposed in the atomic layer deposition reaction chamber. The microbalance is used for placing a thermosensitive material and collecting the growth rate of the film thickness on the thermosensitive material.

[0011] The first gas channel is connected to the atomic layer deposition reaction chamber. The first gas channel is used for delivering a metal precursor to the atomic layer deposition reaction chamber.

[0012] The second gas channel is connected to the plasma gas reaction chamber. The second gas channel is used for delivering a preset gas to the plasma gas reaction chamber.

[0013] Preferably, the microbalance is a quartz crystal microbalance.

[0014] Preferably, the metal precursor can at least include one or more of a bidentate ligand aluminum precursor, a tin precursor, a titanium precursor, and a zinc precursor.

[0015] Preferably, the device can further include a monitoring unit; the monitoring unit is connected to the microbalance, and the monitoring unit is at least used for acquiring and displaying the growth rate information collected by the microbalance.

[0016] Preferably, the device can further include a radio frequency generator;

[0017] The radio frequency generator is connected to the plasma gas reaction chamber. The radio frequency generator is used for providing radio frequency power to the radio frequency coil of the plasma gas reaction chamber.

[0018] Preferably, the preset gas can include at least one or more of oxygen, nitrogen, and argon.

[0019] Preferably, flow meters are provided on both the first gas channel and the second gas channel; the flow meters are used for monitoring the gas flow in the gas channels.

[0020] In a second aspect, the present invention provides a low-temperature atomic layer deposition method for a thermosensitive material. The method is applied to a low-temperature atomic layer deposition device for a thermosensitive material. The low-temperature atomic layer deposition device for a thermosensitive material at least includes an atomic layer deposition reaction chamber, a plasma gas reaction chamber, a first gas channel, a second gas channel, and a microbalance; the method can include:

[0021] Providing a target thermosensitive material;

[0022] Using the first gas channel and the atomic layer deposition reaction chamber, forming a first deposition layer on the target thermosensitive material; the target thermosensitive material is placed on the microbalance; the microbalance is disposed in the atomic layer deposition reaction chamber;

[0023] Form a second deposition layer on the first deposition layer by using the second gas channel, the plasma gas reaction chamber, and the atomic layer deposition reaction chamber, to obtain a target thin film layer on the target thermosensitive material.

[0024] Preferably, the step of forming a first deposition layer on the target thermosensitive material by using the first gas channel and the atomic layer deposition reaction chamber may include:

[0025] Based on a first pulse timing, use the first gas channel to deliver a metal precursor to the atomic layer deposition reaction chamber;

[0026] And based on a second pulse timing, use the first gas channel to deliver an inert gas to the atomic layer deposition reaction chamber to form the first deposition layer on the target thermosensitive material.

[0027] Preferably, the step of forming a second deposition layer on the first deposition layer by using the second gas channel, the plasma gas reaction chamber, and the atomic layer deposition reaction chamber to obtain a target thin film layer on the target thermosensitive material may include:

[0028] Based on a third pulse timing, use the second gas channel and the plasma gas reaction chamber to deliver a plasma gas to the atomic layer deposition reaction chamber;

[0029] And based on a fourth pulse timing, use the second gas channel and the plasma gas reaction chamber to deliver an inert gas to the atomic layer deposition reaction chamber to form the second deposition layer on the first deposition layer, to obtain a target thin film layer on the target thermosensitive material.

[0030] Compared with the prior art, a low-temperature atomic layer deposition device for a thermosensitive material provided by the present invention includes at least an atomic layer deposition reaction chamber, a plasma gas reaction chamber, a first gas channel, a second gas channel, and a microbalance. The plasma gas reaction chamber is connected to the atomic layer deposition reaction chamber, and the plasma gas reaction chamber is used to generate and transport plasma gas to the atomic layer deposition reaction chamber within a preset time period. The microbalance is disposed in the atomic layer deposition reaction chamber, and is used for the thermosensitive material and to collect the growth rate of the film thickness on the thermosensitive material. The first gas channel is connected to the atomic layer deposition reaction chamber for transporting a metal precursor to the atomic layer deposition reaction chamber. The second gas channel is connected to the plasma gas reaction chamber for transporting a preset gas to the plasma gas reaction chamber. The dissociation temperature of the atomic layer deposition reaction chamber can be reduced to below 120 degrees Celsius, thereby avoiding the problem of thermal deformation of the flexible substrate caused by excessive temperature. At the same time, the growth rate of the film thickness of the oxide film can be monitored by the microbalance, realizing uniform deposition of a low-temperature nanoscale film on the surface of the thermosensitive material, avoiding problems such as insufficient film density in the low-temperature ALD process, improving the yield of the product, and solving the problem of low product yield caused by high-temperature or low-temperature deposition methods in the prior art. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The drawings described herein are used to provide a further understanding of the present invention and form a part of the present invention. The schematic embodiments and descriptions thereof of the present invention are used to explain the present invention and do not constitute an improper limitation of the present invention. In the drawings:

[0032] Figure 1 FIG. is a schematic diagram of the main structure of a low-temperature atomic layer deposition device for a thermosensitive material provided by the present invention;

[0033] Figure 2 FIG. is a schematic diagram of the main process of a low-temperature atomic layer deposition method for a thermosensitive material provided by the present invention.

[0034] Reference numerals: 10 - atomic layer deposition reaction chamber, 20 - plasma gas reaction chamber, 21 - radio frequency coil, 30 - first gas channel, 31 - first flow meter, 40 - second gas channel, 41 - second flow meter, 50 - microbalance, 60 - vacuum pump, 70 - radio frequency generator, 80 - monitoring unit. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0035] In order to facilitate the clear description of the technical solutions of the embodiments of the present invention, in the embodiments of the present invention, the words "first", "second" and the like are used to distinguish the same items or similar items with substantially the same functions and effects. For example, the first threshold and the second threshold are only used to distinguish different thresholds, and do not limit their order of precedence. Those skilled in the art can understand that the words "first", "second" and the like do not limit the quantity and execution order, and the words "first", "second" and the like do not necessarily limit them to be different.

[0036] It should be noted that, in the present invention, words such as "exemplary" or "for example" are used to indicate examples, illustrations or descriptions. Any embodiment or design described as "exemplary" or "for example" in the present invention should not be interpreted as being more preferred or more advantageous than other embodiments or designs. Specifically, the use of words such as "exemplary" or "for example" is intended to present related concepts in a specific way.

[0037] In the present invention, "at least one" means one or more, and "plurality" means two or more. "And / or" describes the association relationship of associated objects, indicating that three relationships may exist. For example, A and / or B can mean: A exists alone, A and B exist at the same time, and B exists alone, where A and B can be singular or plural. The character " / " generally indicates that the associated objects in the previous time are in an "or" relationship. "At least one of the following items" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, at least one of a, b or c can mean: a, b, c, the combination of a and b, the combination of a and c, the combination of b and c, or the combination of a, b and c, where a, b, c can be single or multiple.

[0038] At present, using traditional atomic layer deposition equipment and processes for low-temperature atomic layer deposition or high-temperature atomic layer deposition will result in more or less product quality problems. It has been verified that the main reason is that low-temperature deposition is prone to problems such as insufficient film density and poor water and oxygen barrier properties; while high-temperature deposition is prone to thermal deformation of flexible substrates, making it unsuitable for heat-sensitive substrates; for example, when trimethylaluminum (TMA) is used as a precursor for atomic layer deposition, since the dissociation efficiency of the trimethylaluminum precursor TMA (Al(CH3)3) is low at low temperatures (<150°C), high temperatures (greater than 200 degrees Celsius) are required to activate it in order to improve its reaction activation. In this case, thermal deformation of the flexible substrate is likely to occur, so it is not suitable for heat-sensitive substrates; and dissociation at low temperatures will result in insufficient dissociation, which will cause the generated film to easily produce pinhole defects and a roughness RMS>2nm, thereby reducing the yield rate of the product.

[0039] Therefore, to solve the problem that low product yield occurs when high-temperature or low-temperature deposition is carried out on heat-sensitive materials, the present invention provides a low-temperature atomic layer deposition device and method for heat-sensitive materials, which can reduce the dissociation temperature of the atomic layer deposition reaction chamber to below 120 degrees Celsius, and can monitor the film thickness growth rate of the oxide film, realizing uniform deposition of low-temperature nanoscale films on the surface of heat-sensitive materials and improving the product yield.

[0040] Next, the technical solutions of the present invention will be described in detail with reference to the accompanying drawings:

[0041] Please refer to Figure 1 , Figure 1 which is a schematic diagram of the main structure of a low-temperature atomic layer deposition device for heat-sensitive materials provided by the present invention.

[0042] In Figure 1 , the device may at least include an atomic layer deposition reaction chamber 10, a plasma gas reaction chamber 20, a first gas channel 30, a second gas channel 40, a microbalance 50, and a vacuum pump 60.

[0043] Specifically, after connecting the plasma gas reaction chamber 20 to the atomic layer deposition reaction chamber 10, the plasma gas reaction chamber 20 is used to generate and transport plasma gas to the atomic layer deposition reaction chamber within a preset time period; the microbalance 50 is arranged in the atomic layer deposition reaction chamber 10, and the microbalance 50 can be used to place heat-sensitive materials and collect the growth rate of the film thickness on the heat-sensitive materials; preferably, a heating device is also arranged in the microbalance 50, so that the microbalance 50 can provide the heat required for the reaction for the heat-sensitive material sample placed on it; the setting method of its heating device can be on the upper layer, inside or lower layer of the microbalance, which is not specifically limited in the present invention.

[0044] Furthermore, the first gas channel 30 can be connected to the atomic layer deposition reaction chamber 10, and the first gas channel 30 is used to transport metal precursors to the atomic layer deposition reaction chamber 10, so that when an inert gas is transported through the first channel, the metal precursor can be brought into the atomic layer deposition reaction chamber 10 for purging, and atomic layer deposition can be carried out on the surface of the heat-sensitive material placed on the microbalance.

[0045] Furthermore, the second gas channel 40 can be connected to the plasma gas reaction chamber 20, and the second gas channel 40 is used to transport a preset gas to the plasma gas reaction chamber 20, so that when an inert gas is transported through the second channel, the preset gas can be brought into the plasma gas reaction chamber 20 for ionization and then transported to the atomic layer deposition reaction chamber 10 for purging, and further atomic layer deposition can be carried out on the heat-sensitive material.

[0046] Furthermore, a vacuum pump 60 can be connected to the atomic layer deposition reaction chamber 10, so as to provide a high-vacuum environment for the atomic layer deposition reaction chamber 10 by using the vacuum pump 60.

[0047] Based on this, a low-temperature atomic layer deposition device for a thermosensitive material provided by the present invention can reduce the dissociation temperature of the atomic layer deposition reaction chamber to below 120 °C, thereby avoiding the problem of thermal deformation of the flexible substrate caused by too high temperature; at the same time, a microbalance can be used to monitor the film thickness growth rate of the oxide film, realizing uniform deposition of a low-temperature nanoscale film on the surface of the thermosensitive material, avoiding problems such as insufficient film density in the low-temperature ALD process, improving the yield of products, and solving the problem of low product yield caused by high-temperature or low-temperature deposition methods in the prior art.

[0048] Preferably, the microbalance can be a quartz crystal microbalance. The quartz crystal microbalance (QCM) is a surface-sensitive analysis technology based on the piezoelectric effect of quartz crystals. It is a very sensitive mass detection instrument with a measurement accuracy up to the nanogram level. It can be used to monitor and characterize (bio)film deposition, detect specific antigens, study biomolecular binding kinetics, cell adhesion and DNA detection, and measure the interaction of molecules, polymers and biological components on the sensor surface in air or label-free liquids in real time. Its working principle is based on the change in the resonance frequency of the quartz crystal sensor when covered with a film or liquid.

[0049] The present invention integrates a quartz crystal microbalance (QCM) in the atomic layer deposition reaction chamber, utilizes the piezoelectric effect of quartz crystals, converts the change in the mass on the surface of the quartz crystal electrode into the change in the frequency of the electrical signal output by the quartz crystal oscillation circuit, and then high-precision data can be obtained through other auxiliary devices such as a computer; thus, the film thickness growth rate can be monitored in real time, and the film thickness accuracy can be controlled within ±0.1 nm.

[0050] Preferably, the metal precursor can at least include one or more of a bidentate ligand aluminum as a precursor, a tin precursor, an aluminum precursor, a titanium precursor, and a zinc precursor; the above metal precursors can be set according to requirements as long as they can meet the low-temperature deposition of the thermosensitive material.

[0051] Preferably, a low-temperature atomic layer deposition device for a thermosensitive material provided by the present invention can further include a monitoring unit 80; the monitoring unit 80 is connected to the microbalance 50, and the monitoring unit 80 is at least used to acquire and display the growth rate information collected by the microbalance 50. It should be noted that the monitoring unit 80 can be fixed on the panel of the low-temperature atomic layer deposition device or a remote computer, and no specific limitation is made in the present invention.

[0052] Preferably, a low-temperature atomic layer deposition apparatus for a thermosensitive material provided by the present invention may further include a radio frequency generator 70; the radio frequency generator 70 is connected to the plasma gas reaction chamber 20, and the radio frequency generator 70 is used to provide radio frequency power to the radio frequency coil 21 of the plasma gas reaction chamber 20; thereby realizing the generation of plasma gas by using the plasma gas reaction chamber 20.

[0053] Preferably, the preset gas may include at least one or more of oxygen, nitrogen, and argon. The type of gas can be determined according to the type of the thermosensitive material and / or the metal precursor; oxygen is preferably used as the preset gas in the present invention.

[0054] Preferably, flow meters may be provided on both the first gas channel and the second gas channel; the flow meters are used to monitor the gas flow rate in the gas channel. Specifically, a first flow meter 31 may be provided on the first gas channel 30, and the first flow meter 31 is used to monitor the gas flow rate in the first gas channel 30; a second flow meter 41 may be provided on the second gas channel 40, and the second flow meter 41 is used to monitor the gas flow rate in the second gas channel 40; thereby effectively monitoring the gas flow velocity in the gas channel to better complete atomic layer deposition and achieve a better deposition effect.

[0055] To further illustrate the technical effects of a low-temperature atomic layer deposition apparatus for a thermosensitive material provided by the present invention, as an example, bis-ligand aluminum [Al(acac)_2(OPr)_2] is used as a precursor in the present invention for illustration.

[0056] It can be obtained through thermogravimetric analysis verification by a TGA thermogravimetric analyzer that: the dissociation temperature of the bis-ligand aluminum precursor can be reduced to 80 °C, and the temperature resistance limit of the flexible substrate is less than or equal to 120 °C. Therefore, the bis-ligand aluminum precursor can adapt to the temperature resistance limit of the flexible substrate. And the bis-ligand aluminum precursor has high surface reaction activity, and the single-cycle deposition rate reaches

[0057] Furthermore, by using a low-temperature atomic layer deposition apparatus for a thermosensitive material provided by the present invention, the preparation process parameters are optimized, so that the atomic layer deposition environment temperature can be lowered to below 120 °C to perform low-temperature atomic layer deposition on the thermosensitive material, as shown in Tables 1 to 2.

[0058] Table 1 Process optimization table of a low-temperature atomic layer deposition apparatus for a thermosensitive material provided by the present invention

[0059] Serial number Parameter Range Optimal value 1 Reaction temperature 80-120℃ 90℃ 2 Precursor pulse time 0.05-0.2s 0.1s 3 Plasma power 50-200W 100W

[0060] Table 2 Comparison table of the film properties deposited at an atomic layer deposition environment temperature of 90 °C and the film properties deposited by the traditional process

[0061] Serial number Performance parameter Process of the present invention (90 °C) Traditional process (200 °C) 1 Thickness uniformity (±%) 1.2 3.8 2 Surface roughness (RMS, nm) 0.5 - 0.8 nm ≥2.3 3 Water and oxygen barrier (WVTR) <![CDATA[5×10 -6 g / m 2 / day]]> <![CDATA[1×10 -3 g / m 2 / day]]>

[0062] It can be undoubtedly obtained from Table 1 to Table 2 that after setting the equipment operation parameters of a low-temperature atomic layer deposition equipment for a thermosensitive material provided by the present invention according to Table 1, the obtained thin film layer; its film roughness (RMS) is 0.5 - 0.8 nm, compared with that of the traditional process which is greater than or equal to 2.3 nm, so that the island growth mode can be suppressed by using short pulses + laminar flow purge; and the water and oxygen barrier performance is WVTR of 5×10 -6 g / m 2 / day, less than 1×10 -5 g / m 2 / day, and the water and oxygen barrier performance of the uncoated PET in the traditional process is improved by at least 10 3 times. This dense and pinhole-free structure can block the water and oxygen diffusion path; it can be seen that the thickness uniformity of the thin film layer prepared by using the equipment of the present invention is significantly improved, the film roughness is significantly reduced, and the water and oxygen barrier performance is improved, greatly improving the product yield rate.

[0063] Furthermore, a low-temperature atomic layer deposition equipment for a thermosensitive material provided by the present invention can be used to prepare a flexible OLED encapsulation layer; the parameter settings are shown in Table 3 for details.

[0064] Table 3 Process Parameter Table for Preparing Flexible OLED Encapsulation Layer

[0065] Serial number Parameter Value 1 Substrate material PET (thickness 100 μm) 2 Reaction temperature 90℃ 3 Precursor Al(acac)_2(OPr)_2 4 Number of cycles 600 times 5 Film thickness 52.3 ± 1.2 nm

[0066] Furthermore, after setting the parameters in Table 3 for a low-temperature atomic layer deposition equipment for a thermosensitive material provided by the present invention, a flexible OLED encapsulation layer is prepared, and the target flexible OLED is obtained; after performing performance tests on the target flexible OLED, the performance test results are as follows:

[0067] 1. Water and oxygen barrier property (aged at 85°C / 85% RH for 1000 hours): No delamination phenomenon.

[0068] 2. Transmittance: >92% (visible light band).

[0069] It is further explained that by using a low-temperature atomic layer deposition equipment for a thermosensitive material provided by the present invention, the product yield rate is improved, and the problem of low product yield rate caused by high-temperature or low-temperature deposition methods in the prior art is solved.

[0070] Second aspect, the present invention provides a low-temperature atomic layer deposition method for a thermosensitive material, which is applied to a low-temperature atomic layer deposition device for a thermosensitive material, such as the low-temperature atomic layer deposition device for a thermosensitive material disclosed in the first aspect; the low-temperature atomic layer deposition device for a thermosensitive material may at least include an atomic layer deposition reaction chamber, a plasma gas reaction chamber, a first gas channel, a second gas channel, and a microbalance; please refer to Figure 2 , Figure 2 which is a schematic main process diagram of a low-temperature atomic layer deposition method for a thermosensitive material provided by the present invention. The execution subject of the method is a server or a terminal device.

[0071] In Figure 2 , the method may include:

[0072] Step 210: Provide a target thermosensitive material.

[0073] Step 220: Use the first gas channel and the atomic layer deposition reaction chamber to form a first deposition layer on the target thermosensitive material; the target thermosensitive material is placed on the microbalance; the microbalance is arranged in the atomic layer deposition reaction chamber.

[0074] Step 230: Use the second gas channel, the plasma gas reaction chamber, and the atomic layer deposition reaction chamber to form a second deposition layer on the first deposition layer, and obtain a target thin film layer located on the target thermosensitive material.

[0075] In steps 210 to 230, the target thermosensitive material may include materials of types such as polymers, biosensors, flexible electronic devices, etc.; place the target thermosensitive material on the microbalance to ensure that the atomic layer deposition reaction chamber is in a vacuum state; then perform the following operations:

[0076] 1. Set the opening time of the valve for reaction gas 1 (metal precursor, such as a bidentate aluminum precursor) on the first gas channel. During the corresponding time when the valve is opened, reaction gas 1 is introduced into the chamber at the flow rate set by the first flowmeter, and then the valve is closed.

[0077] 2. Use the first channel to transport an inert gas to purge the pipeline and the chamber, and the purging time is also purged according to the program-set time. At this point, half of the reaction of the target thin film layer is completed, and a first deposition layer is obtained.

[0078] 3. Set the opening time of the valve for reaction gas 2 (preset gas, such as oxygen) on the second gas channel. During the corresponding time when the valve is opened, open the valve to introduce reaction gas 2. Reaction gas 2 is introduced into the plasma reaction chamber at the flow rate set by the second flowmeter and is ionized to generate plasma, and then the valve is closed.

[0079] 4. Use the second channel to transport inert gas to purge the pipeline and the cavity. The plasma gas will continue to be introduced into the atomic layer deposition reaction chamber to react with the first deposition layer to form the second deposition layer, that is, the target thin film layer (a thin film layer) located on the target heat-sensitive material is obtained, and a single cycle is completed. Repeat this process, and control the layer thickness required for the reaction according to the weight change of the microbalance to obtain the thin film layer with the final required thickness.

[0080] Experimental verification shows that: the single cycle time of the present invention is 8.2 seconds. Compared with 12 seconds of the traditional process, the efficiency of the present invention is increased by 34%, and the surface coverage rate > 99.5%; further indicating that the technical solution of the present invention brings better technical effects compared with the prior art.

[0081] It should be noted that when the ionization reaction is not carried out, the preset gas can be transported to the atomic layer deposition reaction chamber through the second channel and the plasma gas reaction chamber.

[0082] Based on this, a low-temperature atomic layer deposition method for heat-sensitive materials provided in the second aspect of the present invention can be applied to the low-temperature atomic layer deposition equipment for heat-sensitive materials described in the first aspect, and can achieve uniform deposition of low-temperature nanoscale thin films on the surface of heat-sensitive materials; improve the yield of products, and solve the problem of low product yield caused by high-temperature or low-temperature deposition methods in the prior art.

[0083] Preferably, in step 220, forming the first deposition layer on the target heat-sensitive material by using the first gas channel and the atomic layer deposition reaction chamber may include: based on the first pulse timing, transporting the metal precursor to the atomic layer deposition reaction chamber by using the first gas channel; and based on the second pulse timing, transporting the inert gas to the atomic layer deposition reaction chamber by using the first gas channel to form the first deposition layer on the target heat-sensitive material.

[0084] Exemplarily, the first pulse timing can be set to 0.05 seconds, and the opening time of the valve of reaction gas 1 on the first gas channel can also be 0.05 seconds. The metal precursor (reaction gas 1) is carried into the chamber through the flow rate set by the first flowmeter; a short pulse of 0.05 seconds can reduce excessive adsorption and avoid gas-phase nucleation. Then the second pulse timing is set to 3 seconds, and the inert gas is transported through the first channel to purge the pipeline and the cavity to form the first deposition layer on the target heat-sensitive material. At this point, half of the reaction of the target thin film layer is completed; among them, the inert gas can be nitrogen, and nitrogen can be purged for 3 seconds in the laminar flow mode (Reynolds number Re < 2000) to ensure that the residual precursor is completely removed.

[0085] Preferably, in step 230, a second deposition layer is formed on the first deposition layer by using the second gas channel, the plasma gas reaction chamber, and the atomic layer deposition reaction chamber to obtain a target thin film layer on the target thermosensitive material, which may include: based on a third pulse timing, using the second gas channel and the plasma gas reaction chamber to deliver plasma gas to the atomic layer deposition reaction chamber; and based on a fourth pulse timing, using the second gas channel and the plasma gas reaction chamber to deliver inert gas to the atomic layer deposition reaction chamber to form the second deposition layer on the first deposition layer, thereby obtaining a target thin film layer on the target thermosensitive material.

[0086] Exemplarily, the third pulse timing can be set to 0.1 second, and the opening time of the valve for reaction gas 1 on the second gas channel can also be 0.1 second. Set the opening time of the valve for reaction gas 2 (preset gas, such as oxygen) on the second gas channel, and introduce reaction gas 2 at the corresponding time when the valve is opened. Reaction gas 2 is carried into the plasma reaction chamber under the flow rate set by the second flowmeter and ionized to generate plasma, and then the valve is closed; remote radio frequency plasma (13.56 MHz) can be used to activate the oxygen source to promote the surface oxidation reaction. Further, the fourth pulse timing can be set to 5 seconds, and the inert gas is transported through the second channel to purge the pipeline and the chamber. The plasma gas will continue to be carried into the atomic layer deposition reaction chamber to react with the first deposition layer to form the second deposition layer, that is, a target thin film layer (a thin film layer) on the target thermosensitive material is obtained; pulsed vacuum assistance (pressure instantaneously drops to 0.01 Torr) is achieved, and the film density is improved. Among them, the parameters for generating plasma are preferably: the radio frequency source is 13.56 MHz, and the power density is 1.2 W / cm 2 。

[0087] Although the present invention has been described in conjunction with various embodiments herein, however, in the process of implementing the claimed invention, those skilled in the art can understand and achieve other variations of the disclosed embodiments by viewing the drawings, the disclosure, and the appended claims. In the claims, the word "comprising" does not exclude other components or steps, and "a" or "one" does not exclude a plurality. A single processor or other unit can implement several functions recited in the claims. Certain measures are recited in mutually different dependent claims, but this does not mean that these measures cannot be combined to produce good results.

[0088] Although the present invention has been described in connection with specific features and their embodiments, it will be apparent that various modifications and combinations can be made without departing from the spirit and scope of the invention. Accordingly, the present specification and the drawings are merely exemplary illustrations of the invention defined by the appended claims and are considered to cover any and all modifications, variations, combinations, or equivalents within the scope of the invention. Obviously, those skilled in the art can make various changes and modifications to the present invention without departing from the spirit and scope of the invention. Thus, if these modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalent technologies, the present invention is also intended to include these changes and modifications.

Claims

1. A low-temperature atomic layer deposition device for a thermosensitive material, characterized in that, The device at least includes: an atomic layer deposition reaction chamber, a plasma gas reaction chamber, a first gas channel, a second gas channel, and a microbalance; the plasma gas reaction chamber is connected to the atomic layer deposition reaction chamber, and the plasma gas reaction chamber is configured to generate and deliver a plasma gas to the atomic layer deposition reaction chamber within a preset time period; the microbalance is disposed in the atomic layer deposition reaction chamber, and the microbalance is used to place a heat-sensitive material and collect the growth rate of the film thickness on the heat-sensitive material; the first gas channel is connected to the atomic layer deposition reaction chamber, and the first gas channel is used to deliver a metal precursor to the atomic layer deposition reaction chamber; the second gas channel is connected to the plasma gas reaction chamber, and the second gas channel is used to deliver a preset gas to the plasma gas reaction chamber.

2. The device according to claim 1, characterized in that, The microbalance is a quartz crystal microbalance.

3. The device according to claim 1, characterized in that, The metal precursor at least includes one or more of a bidentate ligand aluminum precursor, a tin precursor, a titanium precursor, and a zinc precursor.

4. The device according to claim 1, characterized in that, The device further includes a monitoring unit; the monitoring unit is connected to the microbalance, and the monitoring unit is at least configured to obtain and display the growth rate information collected by the microbalance.

5. The device according to claim 1, characterized in that, The device further includes a radio frequency generator; the radio frequency generator is connected to the plasma gas reaction chamber, and the radio frequency generator is used to provide radio frequency power to the radio frequency coil of the plasma gas reaction chamber.

6. The device according to claim 1, characterized in that, The preset gas includes at least one or more of oxygen, nitrogen, and argon.

7. The device according to claim 1, characterized in that, Flow meters are disposed on both the first gas channel and the second gas channel; the flow meters are used to monitor the gas flow rate in the gas channels.

8. A low-temperature atomic layer deposition method for a thermosensitive material, characterized in that, The method is applied to a low-temperature atomic layer deposition device for a heat-sensitive material, and the low-temperature atomic layer deposition device for the heat-sensitive material at least includes an atomic layer deposition reaction chamber, a plasma gas reaction chamber, a first gas channel, a second gas channel, and a microbalance; the method includes: providing a target heat-sensitive material; forming a first deposition layer on the target heat-sensitive material by using the first gas channel and the atomic layer deposition reaction chamber; the target heat-sensitive material is placed on the microbalance; the microbalance is disposed in the atomic layer deposition reaction chamber; forming a second deposition layer on the first deposition layer by using the second gas channel, the plasma gas reaction chamber, and the atomic layer deposition reaction chamber to obtain a target thin film layer on the target heat-sensitive material.

9. The method according to claim 8, wherein The forming a first deposition layer on the target heat-sensitive material by using the first gas channel and the atomic layer deposition reaction chamber includes: delivering a metal precursor to the atomic layer deposition reaction chamber by using the first gas channel based on a first pulse timing; and delivering an inert gas to the atomic layer deposition reaction chamber by using the first gas channel based on a second pulse timing to form the first deposition layer on the target heat-sensitive material.

10. The method according to claim 8, characterized in that, Forming a second deposition layer on the first deposition layer by using the second gas channel, the plasma gas reaction chamber, and the atomic layer deposition reaction chamber to obtain a target thin film layer on the target thermosensitive material, including: Based on a third pulse timing sequence, using the second gas channel and the plasma gas reaction chamber to deliver a plasma gas to the atomic layer deposition reaction chamber; And based on a fourth pulse timing sequence, using the second gas channel and the plasma gas reaction chamber to deliver an inert gas to the atomic layer deposition reaction chamber to form the second deposition layer on the first deposition layer, thereby obtaining a target thin film layer on the target thermosensitive material.

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