Film packaging assembly of stretchable electronic device and preparation method thereof
阅读说明：本技术 一种可拉伸电子器件的薄膜封装组件及其制备方法 (Film packaging assembly of stretchable electronic device and preparation method thereof ) 是由 陈蓉 李云 单斌 曹坤 张英豪 林�源 杨惠之 于 2019-10-22 设计创作，主要内容包括：本发明属于电子器件封装领域,并公开了一种可拉伸电子器件的薄膜封装组件及其制备方法。该组件自下而上包括待封装电子器件、阻隔层、光热传导层和疏水防护层,其中,疏水防护层用于阻隔外界的水汽与光热传导层直接接触并进行腐蚀,光热传导层用于增强器件整体透光和散热能力,阻隔层用于进一步阻隔空气中的水和氧气,避免水和氧气进入待封装电子器件,其中,阻隔层包括有机涂层和无机-有机复合层；光热传导层依次包括两个封装层和设置在两个封装层之间的金属散热层。本申请还相应公开了上述封装组件的制备方法。通过本发明所获取的封装组件具备良好的水汽阻隔能力,且兼顾良好的透光性、传热性和拉伸性能,可实现对可拉伸电子器件的长效保护。(The invention belongs to the field of electronic device packaging, and discloses a film packaging assembly of a stretchable electronic device and a preparation method thereof. The assembly comprises an electronic device to be packaged, a blocking layer, a photo-thermal conduction layer and a hydrophobic protection layer from bottom to top, wherein the hydrophobic protection layer is used for blocking external water vapor from directly contacting with the photo-thermal conduction layer and corroding the photo-thermal conduction layer, the photo-thermal conduction layer is used for enhancing the overall light transmission and heat dissipation capacity of the device, the blocking layer is used for further blocking water and oxygen in the air and preventing the water and the oxygen from entering the electronic device to be packaged, and the blocking layer comprises an organic coating and an inorganic-organic composite layer; the photothermal conductive layer sequentially comprises two packaging layers and a metal heat dissipation layer arranged between the two packaging layers. The application also correspondingly discloses a preparation method of the packaging assembly. The packaging assembly obtained by the invention has good water vapor barrier capability, gives consideration to good light transmittance, heat transfer property and tensile property, and can realize long-term protection of the stretchable electronic device.)
1. A thin film package assembly for stretchable electronic devices, the assembly comprising, from bottom to top, an electronic device to be packaged, a barrier layer, a photo-thermal conductive layer and a hydrophobic protective layer, wherein,
the hydrophobic protective layer is used for preventing external water vapor from directly contacting with the photothermal conduction layer to corrode the photothermal conduction layer, the photothermal conduction layer is used for transmitting light and dissipating heat, the barrier layer is used for further blocking water and oxygen in the air and preventing the water and the oxygen from entering the electronic device to be packaged, wherein,
the barrier layer comprises an organic coating (11) and an inorganic-organic composite layer (12), wherein the organic coating (11) is arranged on the electronic device to be packaged, and the inorganic-organic composite layer (12) is a layer formed by compounding an inorganic layer and an organic coating by performing atomic layer filling of the inorganic layer on the surface of the organic coating;
the photothermal conduction layer sequentially comprises two packaging layers (21) and a metal heat dissipation layer (22) arranged between the two packaging layers, wherein the refractive index of the packaging layers (21) is higher than that of the metal heat dissipation layer, so that the medium refractive index of the photothermal conduction layer is in a high-low-high form, the maximum light transmittance is ensured, and the metal heat dissipation layer (22) is used for dissipating heat to avoid aging failure caused by overhigh heat in the working process of the packaged electronic device to be packaged.
2. The thin film encapsulation assembly of a stretchable electronic device according to claim 1, wherein the thickness of the organic coating (11) is preferably 1 μm to 10 μm; the thickness of the inorganic-organic composite layer (12) is preferably 20nm to 50nm, the thickness of the packaging layer (21) is preferably 20nm to 60nm, the thickness of the metal heat dissipation layer (22) is preferably 10nm to 20nm, and the thickness of the hydrophobic protection layer (31) is 1 mu m to 10 mu m.
3. The thin film package assembly of a stretchable electronic device of claim 1, wherein the barrier layer has a barrier capacity of preferably 10 -4～10 -5g/m 2·day。
4. The thin film encapsulation assembly of a stretchable electronic device according to claim 1, wherein the material of the organic coating (11) is preferably PA, PI or PDMS; the inorganic matter in the inorganic-organic composite layer (12) is preferably magnesium oxide, titanium oxide, aluminum oxide or zinc oxide; the packaging layer (21) is preferably a ternary laminated film or a quaternary laminated film, and the ternary laminated film is Al 2O 3/TiO 2、Al 2O 3/MgO、Al 2O 3/ZnO、TiO 2/MgO、TiO 2The quaternary laminated film is Al 2O 3/TiO 2/ZnO、Al 2O 3/ZnO/MgO、Al 2O 3/MgO/TiO 2And MgO/ZnO/TiO 2(ii) a The material of the metal heat dissipation layer (22) is preferably Ag or Al; the material of the organic hydrophobic protective layer (31) is preferably PA or PDMS.
5. A method of making a thin film encapsulation assembly for stretchable electronic devices according to any of claims 1-4, comprising the steps of:
(a) formation of barrier layer
Spin-coating an organic coating on the surface of an electronic device to be packaged, and then curing the organic coating;
performing atomic layer filling on the surface of the organic coating in an atomic layer deposition mode, so that an inorganic substance is filled in atomic gaps of the organic coating, and thus obtaining an inorganic-organic composite layer, namely realizing the formation of the barrier layer;
(b) formation of photothermal conductive layer
Forming an encapsulation layer in the photothermal conduction layer by adopting an atomic deposition method, and forming the metal heat dissipation layer by adopting an evaporation or magnetron sputtering method;
(c) forming hydrophobic protective layers
And coating a layer of hydrophobic protective material on the surface of the photothermal conduction layer, and curing to obtain the required hydrophobic protective layer.
6. The method of claim 5, wherein in step (a), the inorganic-organic composite layer is preferably prepared according to the following steps:
(a1) setting the temperature of the atomic deposition reaction cavity to be 60-100 ℃, starting an air extraction valve to extract the pressure of the reaction cavity to be below 10Pa, and introducing carrier gas to clean the cavity;
(a2) introducing a metal organic precursor pulse, wherein the time length is set to be 0.5-5.0 s, so that the introduction amount of the metal organic precursor is increased, then closing an air extraction valve and the flow of a carrier gas, waiting, and setting the waiting time to be 45-180 s, so that the metal organic precursor is diffused and filled on the surface of the organic coating, wherein the metal organic precursor is trimethylaluminum, diethylzinc, titanium tetrachloride or ethylcyclopentadienyl magnesium;
(a3) opening an extraction valve to extract gas in the reaction cavity, and introducing carrier gas to clean the reaction cavity;
(a4) introducing an oxygen source precursor pulse for 0.5-5.0 s, then closing an air extraction valve and carrier gas flow, and waiting for 45-180 s, so that a metal organic precursor diffused and filled on the surface of the organic coating reacts with the oxygen source precursor to generate an inorganic-organic composite layer, wherein the oxygen source precursor is deionized water or ozone;
(a5) starting to pump out the gas in the reaction cavity, and introducing carrier gas to clean the reaction cavity;
(a6) repeating the steps (a2) - (a5), preferably, the cycle number is 50-100 times, until the thickness of the inorganic-organic composite layer reaches 20-50 nm.
7. The method of claim 5, wherein in step (b), the encapsulation layer is preferably prepared according to the following steps:
(b1) setting the temperature of the reaction cavity to be 90-110 ℃, starting an air extraction valve to extract the pressure of the cavity to be below 10Pa, and introducing carrier gas flow of 50-100 sccm after the pressure is stable.
(b2) Introducing a first metal organic precursor pulse for 0.1-0.5 s, and then waiting for 30-60 s to clean the cavity, wherein the first metal organic precursor is trimethylaluminum, diethyl zinc, titanium tetrachloride or ethylcyclopentadienyl magnesium;
(b3) introducing an oxygen source precursor for 0.1-0.5 s, and then waiting for 30-60 s, wherein the oxygen source is deionized water or ozone;
(b4) introducing a second metal organic precursor pulse for 0.1-0.5 s, and then waiting for 30-60 s, wherein the second metal organic precursor is different from the first metal organic precursor and forms a composite phase with the first metal organic precursor, and the second metal organic precursor is trimethylaluminum, diethylzinc, titanium tetrachloride or ethylmagnesium metallocene;
(b5) introducing an oxygen source precursor for 0.1-0.5 s, and then waiting for 30-60 s, wherein the oxygen source is deionized water or ozone;
(b6) repeating steps (b2) - (b5), preferably 200-600 times, until the thickness of the resulting package layer is about 20-60 nm.
8. The method of claim 5, wherein in the step (b), the degree of vacuum in the reaction chamber is not higher than 5 x 10 during the process of preparing the metal heat dissipation layer -4Pa, used for ensuring the purity of the metal heat dissipation layer.
Technical Field
The invention belongs to the field of electronic device packaging, and particularly relates to a film packaging assembly of a stretchable electronic device and a preparation method thereof.
Background
Flexible electronics are highly appreciated by consumers and manufacturers for their unique flexibility, extensibility, portability, and low manufacturing cost. Particularly, with the rapid development of stretchable electronics, the rapid rise of product fields such as wearable electronic products, electronic skins, implantable medical electronic devices, soft robots and the like is greatly promoted. In the practical production and application process of related products, electrode materials, organic functional materials and the like are extremely easy to be corroded by water and oxygen in the air atmosphere, and further performance of devices is reduced and service life of the devices is shortened. The search for a packaging function with good flexibility, barrier property and tensile property is significant for promoting the development of related industries.
The current commercial metal/encapsulation methods are not applicable to the encapsulation of stretchable electronic devices because they are not flexible and extensible. When the ultra-thin metal foil is used for packaging, although the ductility is still good, the light emitting performance of the related optoelectronic device is reduced. At present, the thin film encapsulation method developed based on the chemical vapor deposition technology and the like has become a hot spot of research in the industry and academia.
In the thin film packaging technology, the inorganic dielectric material can realize effective blocking of water vapor, but is hard and brittle, and is easy to break and lose efficacy under frequent bending and stretching conditions; however, although the organic material has good bending and stretching properties, it cannot prevent water vapor from diffusing into the interior. Therefore, the existing film packaging method mainly takes an organic-inorganic laminated structure to fully exert the advantages of different materials in the aspects of mechanics and barrier property. However, the method mainly focuses on optimization of barrier property and bending property of the packaging structure, has a small strain degree, cannot meet the requirements of the stretchable electronic device, and research and application of the method in the stretchable electronic packaging aspect are rarely reported in the prior art.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a film packaging assembly of a stretchable electronic device and a preparation method thereof.
To achieve the above objects, according to one aspect of the present invention, there is provided a thin film encapsulation assembly for a stretchable electronic device, the assembly including, from bottom to top, an electronic device to be encapsulated, a barrier layer, a photothermal conductive layer and a hydrophobic protective layer, wherein,
the hydrophobic protective layer is used for preventing external water vapor from directly contacting with the photothermal conduction layer to corrode the photothermal conduction layer, the photothermal conduction layer is used for transmitting light and dissipating heat, the barrier layer is used for further blocking water and oxygen in the air and preventing the water and the oxygen from entering the electronic device to be packaged, wherein,
the barrier layer comprises an organic coating and an inorganic-organic composite layer, wherein the organic coating is arranged on the electronic device to be packaged, and the inorganic-organic composite layer is a layer formed by compounding an inorganic substance and an organic coating through atomic layer filling of the inorganic substance on the surface of the organic coating;
the photothermal conduction layer sequentially comprises two packaging layers and a metal heat dissipation layer arranged between the two packaging layers, wherein the refractive index of the packaging layers is higher than that of the metal heat dissipation layer, so that the medium refractive index of the photothermal conduction layer is in a high-low-high form, the maximum light transmittance is ensured, and the metal heat dissipation layer is used for dissipating heat to avoid aging failure caused by overhigh heat in the working process after the electronic device is packaged.
Further preferably, the thickness of the organic coating layer is preferably 1 μm to 10 μm; the inorganic-organic composite layer preferably has a thickness of 20nm to 50nm, the encapsulation layer preferably has a thickness of 20nm to 60nm, the metal heat dissipation layer preferably has a thickness of 10nm to 20nm, and the hydrophobic protection layer preferably has a thickness of 1 μm to 10 μm.
Further preferably, the barrier capability of the barrier layer can reach 10 -4～10 -5g/m 2·day。
Further preferably, the material of the organic coating is preferably PA, PI or PDMS; the inorganic matter in the inorganic-organic composite layer is preferably magnesium oxide, titanium oxide, aluminum oxide or zinc oxide; the packaging layer is preferably a ternary laminated film or a quaternary laminated film, and the ternary laminated film is Al 2O 3/TiO 2、Al 2O 3/MgO、Al 2O 3/ZnO、TiO 2/MgO、TiO 2/ZnO or MgO/ZnO, the quaternary laminated film comprises Al 2O 3/TiO 2/ZnO、Al 2O 3/ZnO/MgO、Al 2O 3/MgO/TiO 2And MgO/ZnO/TiO 2(ii) a The material of the metal heat dissipation layer is preferably Ag or Al; the material of the organic hydrophobic protective layer is preferably PA or PDMS.
According to another aspect of the present invention, there is provided a method for preparing a thin film encapsulation assembly for a stretchable electronic device as described above, the method comprising the steps of:
(a) formation of barrier layer
Spin-coating an organic coating on the surface of an electronic device to be packaged, and then curing the organic coating;
performing atomic layer filling on the surface of the organic coating in an atomic layer deposition mode, so that an inorganic substance is filled in atomic gaps of the organic coating, and thus obtaining an inorganic-organic composite layer, namely realizing the formation of the barrier layer;
(b) formation of photothermal conductive layer
Forming an encapsulation layer in the photothermal conduction layer by adopting an atomic deposition method, and forming the metal heat dissipation layer by adopting an evaporation or magnetron sputtering method;
(c) forming hydrophobic protective layers
And coating a layer of hydrophobic protective material on the surface of the photothermal conduction layer, and curing to obtain the required hydrophobic protective layer.
Further preferably, in step (a), the preparation of the inorganic-organic composite layer is preferably performed according to the following steps:
(a1) setting the temperature of the atomic deposition reaction cavity to be 60-100 ℃, starting an air extraction valve to extract the pressure of the reaction cavity to be below 10Pa, and introducing carrier gas to clean the cavity;
(a2) introducing a metal organic precursor pulse, wherein the time length is set to be 0.5-5.0 s, so that the introduction amount of the metal organic precursor is increased, then closing an air extraction valve and the flow of a carrier gas, waiting, and setting the waiting time to be 45-180 s, so that the metal organic precursor is diffused and filled on the surface of the organic coating, wherein the metal organic precursor is trimethylaluminum, diethylzinc, titanium tetrachloride or ethylcyclopentadienyl magnesium;
(a3) opening an extraction valve to extract gas in the reaction cavity, and introducing carrier gas to clean the reaction cavity;
(a4) introducing an oxygen source precursor pulse for 0.5-5.0 s, then closing an air extraction valve and carrier gas flow, and waiting for 45-180 s, so that a metal organic precursor diffused and filled on the surface of the organic coating reacts with the oxygen source precursor to generate an inorganic-organic composite layer, wherein the oxygen source precursor is deionized water or ozone;
(a5) starting to pump out the gas in the reaction cavity, and introducing carrier gas to clean the reaction cavity;
(a6) repeating the steps (a2) - (a5), preferably, the cycle number is 50-100 times, until the thickness of the inorganic-organic composite layer reaches 20-50 nm.
Further preferably, in step (b), the encapsulation layer is preferably prepared according to the following steps:
(b1) setting the temperature of the reaction cavity to be 90-110 ℃, starting an air extraction valve to extract the pressure of the cavity to be below 10Pa, and introducing carrier gas flow of 50-100 sccm after the pressure is stable.
(b2) Introducing a first metal organic precursor pulse for 0.1-0.5 s, and then waiting for 30-60 s to clean the cavity, wherein the first metal organic precursor is trimethylaluminum, diethyl zinc, titanium tetrachloride or ethylcyclopentadienyl magnesium;
(b3) introducing an oxygen source precursor for 0.1-0.5 s, and then waiting for 30-60 s, wherein the oxygen source is deionized water or ozone;
(b4) introducing a second metal organic precursor pulse for 0.1-0.5 s, and then waiting for 30-60 s, wherein the second metal organic precursor is different from the first metal organic precursor and forms a composite with the first metal organic precursor, and the second metal organic precursor is trimethylaluminum, diethylzinc, titanium tetrachloride or ethylmagnesium dicyclopentadienyl;
(b5) introducing an oxygen source precursor for 0.1-0.5 s, and then waiting for 30-60 s, wherein the oxygen source is deionized water or ozone;
(b6) repeating steps (b2) - (b5), preferably 200-600 times, until the thickness of the resulting package layer is about 20-60 nm.
Further preferably, in the step (b), during the preparation of the metal heat dissipation layer, the degree of vacuum in the reaction chamber is not higher than 5 × 10 -4Pa, used for ensuring the purity of the metal heat dissipation layer.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
1. the composite packaging film disclosed by the invention takes an organic film material with excellent mechanical properties as a main body, has good tensile property, and is modified on the surface of an organic coating by utilizing an atomic layer deposition method to obtain an inorganic-organic composite layer, wherein the diffusion and filling effects of a precursor in the organic film are obviously improved in a mode of prolonging the pulse time of a metal and oxygen source precursor, closing the gas flow and an air extraction valve after the precursor is introduced, the organic film is fully filled through multiple cycles, and the water vapor barrier capability of the organic film is obviously improved; compared with the existing inorganic layer growing on the surface of the organic coating, when the encapsulated electronic device is stretched, the inorganic-organic composite layer cannot be broken, and external water and oxygen cannot easily permeate inwards;
2. according to the invention, the photo-thermal conductive layer and the metal heat dissipation layer are inserted into the packaging layer, and the formed inorganic dielectric-metal-inorganic dielectric three-dimensional structure forms a high-low-high refractive index form, so that reflection can be effectively reduced, further the light transmittance is improved, and the influence on the light emitting performance of the stretchable display device can be reduced as much as possible when the stretchable display device is applied;
3. the top organic hydrophobic protective layer has good hydrophobic property, and can effectively reduce the adsorption of water vapor on the surface of the packaging structure under the high-temperature and high-humidity condition, so as to protect the internal inorganic material. In addition, the organic coating can further enhance the flexibility and the tensile property of the packaging structure and prevent the internal inorganic barrier material from being mechanically damaged by external scratches and the like;
4. the organic-inorganic dielectric-metal-inorganic dielectric-organic composite packaging structure formed by the packaging assembly provided by the invention has the advantages that the layers form good interface contact and are tightly combined with the surface of a device, different functional layers are mutually coupled, the defect density can be effectively reduced, the water and oxygen transmission path can be prolonged, the total thickness is 2-20 mu m, and the barrier capability is equivalent to that of a glass/metal cover plate in the practical application process.
Drawings
Figure 1 is a schematic structural view of a thin film package assembly for a stretchable electronic device constructed in accordance with a preferred embodiment of the present invention;
figure 2 is a flow chart of the preparation of a thin film package assembly for a stretchable electronic device constructed in accordance with a preferred embodiment of the present invention;
FIG. 3 is a pictorial representation of an encapsulated stretchable electronic device constructed in accordance with a preferred embodiment of the present invention;
fig. 4 is a comparison of the light emission state of an electronic device constructed in accordance with a preferred embodiment of the present invention, wherein (a) is the initial state of the electronic device, the light emission state is 720 hours after the electronic device is packaged, and the light emission state is 2 hours after the unpackaged electronic device is aged;
FIG. 5 is a comparison of surface topography before and after stretching of an encapsulated electronic device constructed in accordance with a preferred embodiment of the present invention, wherein (a) is a microscopic surface topography view before and (b) is a microscopic surface topography view after a tensile test of the encapsulated electronic device;
fig. 6 is a diagram of a light transmittance test structure of a packaged electronic device constructed in accordance with a preferred embodiment of the present invention.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:
40-electronic device, 50-substrate of electronic device, 11-organic coating, 12-inorganic-organic composite layer, 21-packaging layer, 22-metal heat dissipation layer, 31-organic hydrophobic protection layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
As shown in fig. 1, the embodiment of the present invention provides a thin film encapsulation assembly for stretchable electronic devices, which includes an electronic device to be encapsulated, the electronic device includes a
The thickness of the organic coating is preferably 1-10 μm, which is convenient for filling, and if the thickness is too thin, the inorganic-organic composite layer can penetrate through the organic coating in the filling process, and if the thickness is too thick, the load of the electronic device can be increased; the thickness of the inorganic-organic composite layer is preferably 20nm to 50 nm; the thickness of the packaging layer is preferably 20 nm-60 nm, the thickness of the packaging layer is matched with that of the metal heat dissipation layer, so that the light transmittance of the photothermal conduction layer is maximized, the thickness of the metal heat dissipation layer is preferably 10 nm-20 nm, and if the thickness of the metal heat dissipation layer is too thin, the thin film is discontinuous, namely the heat dissipation of the electronic device is uneven, and if the thickness of the metal heat dissipation layer is too thick, the light transmittance is poor; the thickness of the hydrophobic protective layer is 1-10 μm, and the hydrophobic layer is too thin to reduce the efficacy of water vapor isolation, and too thick to increase the thickness of the whole packaging assembly.
The barrier layer comprises an organic coating and an inorganic-organic composite layer formed by atomic layer filling on the surface of the organic coating, so that the barrier capability of the barrier layer is 10 times of the original barrier capability -110 to 10 -4～10 -5g/m 2·day。
The material of the organic coating is preferably PA, PI or PDMS; the inorganic substance in the inorganic-organic composite layer is preferably magnesium oxide, titanium oxide, aluminum oxide or zinc oxide; the packaging layer is preferably a ternary laminated film or a quaternary laminated film, and the ternary laminated film comprises Al 2O 3/TiO 2、Al 2O 3MgO and Al 2O 3/ZnO, the quaternary laminated film comprises Al 2O 3/TiO 2/ZnO and Al 2O 3/ZnO/MgO; metal heat dissipation layerThe material of (b) is preferably Ag or Al; the material of the organic hydrophobic protective layer is preferably PA or PDMS.
As shown in fig. 2, a method for preparing a thin film encapsulation assembly for a stretchable electronic device includes the steps of:
s1, preparing a micron-sized organic coating on the surface of the electronic device to be packaged and curing the coating.
In the above step, the micron-sized organic coating may be made of an organic material having good tensile properties and light transmittance, such as, but not limited to, Polyamide (PA), Polyimide (PI), Polydimethylsiloxane (PDMS), and the like, and may have a thickness of 1-10 μm by spin coating or doctor blade method. After the preparation is finished, the substrate is transferred to an ALD cavity for curing, the cavity is vacuumized to be below 10Pa, the heating temperature is 50-100 ℃, and the curing time is 30 min.
Preferably, the rotating speed is controlled to be 1000-4000 r/min during spin coating.
And S2, optimizing the atomic layer deposition process to modify the near surface of the micron-sized organic coating to form an inorganic-organic composite layer.
After the organic coating is cured, the heating temperature of the cavity is set to be 60-100 ℃. And vacuumizing the reaction cavity, and introducing carrier gas to clean the cavity. After cleaning, a metal organic precursor and an oxygen source precursor are alternately introduced to modify the near surface of the organic coating to form an organic-inorganic composite layer, so that the barrier property of the organic-inorganic composite layer is improved while the tensile property is ensured. The method specifically comprises the following steps:
s21, setting the temperature of the cavity to be 60-100 ℃, starting an air extraction valve to extract the pressure of the cavity to be below 10Pa, and introducing 50-100 sccm of carrier gas flow after stabilization;
s22, introducing a metal organic precursor pulse for 0.5-5.0S, increasing the introduction amount, then closing an air extraction valve and the flow of a carrier gas, and waiting for 45-180S, so that the metal organic precursor is diffused and filled on the surface of the organic coating;
s23, starting the air extraction valve for waiting for 30-60S, introducing carrier gas with the flow rate of 50-100 sccm after the waiting is finished, and then waiting for 30-90S. The carrier gas flow is used for cleaning the cavity;
s24, introducing oxygen source precursor pulses for 0.5-5.0S, and then closing the extraction valve and the carrier gas flow for waiting. The waiting time is 45-180 s, so that a metal organic precursor diffused and filled on the surface of the organic coating reacts with the oxygen source to generate an inorganic-organic composite layer;
s25, starting the air extraction valve for waiting for 30-60S, introducing carrier gas with the flow rate of 50-100 sccm after the waiting is finished, and then waiting for 30-90S;
s26 repeating the steps S22-S25, preferably, the circulation times are 50-100 times, so that the thickness of the inorganic-organic composite layer reaches 20-50 nm.
Preferably, before the preparation of the photothermal conduction layer is started, the pressure of the reaction cavity is below 10Pa when the carrier gas is not introduced for vacuumizing, and the pressure of the reaction cavity is between 150 Pa and 400Pa after the carrier gas is introduced, so that the vacuum state of the reaction cavity is ensured.
Preferably, the metal precursor combination selected includes, but is not limited to, Trimethylaluminum (TMA)/H 2O, Trimethylaluminum (TMA)/O 3Diethyl zinc (DEZn)/H 2O、TiCl 4/H 2O、Mg(EtCp) 2/H 2O, etc.; the precursor of the oxygen source is deionized water or ozone.
The S3 step is used to prepare an encapsulation layer with good barrier properties and corrosion resistance.
After the preparation of the organic coating near-surface modification layer is finished, the temperature of the cavity is set to be 90-110 ℃. And opening an air extraction valve and the gas flow of the precursor to clean the cavity, and alternately introducing a metal organic precursor 1/an oxygen source precursor/a metal organic precursor 2/an oxygen source precursor and the like after cleaning is finished, wherein the process is a single cycle. The thickness of the grown film is controlled by controlling the number of cycles, the prepared packaging layer has good water oxygen barrier capability and chemical stability, the formation of the composite phase of the packaging layer can effectively inhibit the crystallization of the film and reduce the density of pinholes, and the packaging layer has good acid-base corrosion resistance, and the method comprises the following specific steps:
s31, setting the temperature of the cavity to be 90-110 ℃, starting the air extraction valve to extract the pressure of the cavity to be below 10Pa, and introducing 50-100 sccm of carrier gas flow after stabilization.
S32, introducing a first metal organic precursor pulse for 0.1-0.5S, wherein the amount of the precursor introduced by the pulse is enough to form saturated adsorption on the surface of the packaging structure, so that the precursor utilization rate is not too low, and then waiting for 30-60S to clean the cavity.
And S33, introducing an oxygen source precursor for 0.1-0.5S, and then waiting for 30-60S.
S34, introducing a second metal organic precursor pulse for 0.1-0.5S, and then waiting for 30-60S.
And S35, introducing an oxygen source precursor for 0.1-0.5S, and then waiting for 30-60S.
S36 repeating S32-S35, preferably, the cycle number is 200-600 times, until the thickness of the inorganic nano-laminated film is about 20-60 nm.
Preferably, in the preparation process of the packaging layer, the pressure of the cavity of the reaction cavity is below 10Pa when the cavity is not filled with the carrier gas for vacuumizing, and the pressure of the cavity is between 150 Pa and 400Pa after the carrier gas is filled, so that the vacuum state in the reaction cavity is ensured.
Preferably, in this step, the first metal organic precursor is trimethyl aluminum, titanium tetrachloride, ethyldimocene magnesium, diethyl zinc, or the like, and the second metal organic precursor is one of trimethyl aluminum, titanium tetrachloride, ethyldimocene magnesium, and diethyl zinc, but is different from the first metal organic precursor. And the oxygen source precursor is one of deionized water or ozone. This step may further introduce a third metal organic precursor, which is different from both the first and second materials, which may be trimethylaluminum, titanium tetrachloride, ethylmagnesium metallocene, or diethylzinc.
The step S4 is for preparing a metal layer material having good flexibility and heat dissipation capability.
After the first layer of inorganic nano laminated film structure is prepared, the first layer of inorganic nano laminated film structure is transferred to an evaporation cavity (or magnetron sputtering and the like) to complete the preparation of the metal heat dissipation layer, so that the heat under the working condition of the device can be transferred to the atmospheric environment.
Preferably, the background pressure of the chamber is pumped to 5 × 10 before starting evaporation -4Pa and below
Preferably, the metal silver particles (or aluminum, etc.) to be evaporated are placed in a molybdenum or tungsten boat, etc., and a strong current is applied on both sides, which is increased incrementally at a rate of 5A/min, until the thickness of the quartz crystal begins to increase continuously, monitored on a microscopic day.
Preferably, the shutter is opened and the evaporation rate is controlled to be The thickness of the metal layer is controlled to be 10-20 nm. When the film is too thin, it is liable to cause uneven heat dissipation due to discontinuity, and when it is too thick, it causes poor light transmittance.
The S5 step completes the preparation of the second inorganic nano laminated film after completing the preparation of the metal heat dissipation layer using the same process steps as S3.
Step S6 is to prepare a top organic protective coating layer with hydrophobic properties by spin coating or doctor blading.
In the preparation process of the composite packaging layer, the reaction temperature of the cavity is always controlled below 100 ℃, so that the damage of high temperature to organic sensitive materials in the stretchable electronic material can be effectively prevented.
The present invention will be further illustrated with reference to specific examples.
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