CN112420970B - Method for protecting and etching anode side wall of silicon-based Micro OLED Micro-display device - Google Patents
Method for protecting and etching anode side wall of silicon-based Micro OLED Micro-display device Download PDFInfo
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- 238000005530 etching Methods 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 56
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 11
- 239000010703 silicon Substances 0.000 title claims abstract description 11
- 238000001039 wet etching Methods 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims description 57
- 238000001312 dry etching Methods 0.000 claims description 16
- 238000007747 plating Methods 0.000 claims description 15
- 229920002120 photoresistant polymer Polymers 0.000 claims description 9
- 239000003292 glue Substances 0.000 claims description 7
- 238000001259 photo etching Methods 0.000 claims description 6
- 238000004544 sputter deposition Methods 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 3
- 238000004026 adhesive bonding Methods 0.000 claims description 2
- 238000001459 lithography Methods 0.000 claims 1
- 238000002310 reflectometry Methods 0.000 abstract description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 2
- 239000004332 silver Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 40
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000002253 acid Substances 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 238000010586 diagram Methods 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- 230000000802 nitrating effect Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
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Abstract
The invention provides a method for protecting and etching the side wall of an anode of a silicon-based Micro OLED Micro display device, which belongs to an etching method for protecting the side wall by etching back during silver wet etching, and the method can reduce the CD loss of Ag wet etching from 1 mu m to less than 0.1 mu m, greatly improve the precision of the Ag wet etching, enable the anode to adopt an Ag structure, effectively improve the reflectivity of the anode and greatly improve the luminous efficiency of the device.
Description
Technical Field
The invention belongs to the field of silicon-based Micro OLED Micro display, and particularly relates to a method for protecting and etching the side wall of an anode of a silicon-based Micro OLED Micro display device.
Background
In order to meet the requirement of high PPI, the silicon-based Micro OLED Micro display device anode structure needs to meet the requirement of high-precision process. The high-precision process is completed by matching photoetching with etching, and because the wet etching has larger CD loss and the precision is far worse than that of the dry etching, the current anode etching is carried out by adopting the dry etching process. In order to match with the dry etching process, the anode material needs to be a material easy to dry etch, and the anode material needs to have the properties of high work function, high reflectivity, good conductivity and the like, so the prior anode structure is preferably an ITO + Al + TiN structure. The structure is easy to dry etch, can meet the requirement of high PPI, but has slightly low reflectivity of about 91 percent, and is not an optimal structure. If Ag is adopted to replace anode Al and an ITO + Ag + ITO structure is adopted, the reflectivity can reach 98%, and the luminous efficiency of the device can be greatly improved. However, the difficulty of dry etching of Ag is high, and mass production is not feasible, and the requirement of high-precision process cannot be met due to the large CD loss of wet etching.
Disclosure of Invention
The invention provides a method for protecting and etching the side wall of an anode of a silicon-based Micro OLED Micro display device, which belongs to an etching method for protecting the side wall by etching back during silver wet etching, and the method can reduce the CD loss of Ag wet etching from 1 mu m to less than 0.1 mu m, greatly improve the precision of the Ag wet etching, enable the anode to adopt an Ag structure, effectively improve the reflectivity of the anode and greatly improve the luminous efficiency of the device.
The specific technical scheme of the invention is as follows:
a method for protecting and etching the side wall of an anode of a silicon-based Micro OLED Micro-display device comprises the following steps:
1) Photoetching the substrate 1 with the anode structure coated with ITO + Ag + ITO to perform anode graphical definition to obtain a substrate 2;
2) Wet etching of the upper ITO and Ag layer is carried out on the substrate 2 to obtain a substrate 3;
3) The substrate 3 is deposited with a SiN film layer to obtain a substrate 4;
4) Etching the substrate 4 by adopting a dry etching back etching process, and reserving a SiN film layer on the side wall of the anode to obtain a substrate 5;
5) And (3) carrying out wet etching on the lower layer of ITO on the substrate 5, and then removing the photoresist to obtain a substrate 6.
Further, in step 1), the substrate 1: the film layer structure is ITO + Ag + ITO, the thickness of the upper ITO layer and the lower ITO layer is controlled to be 100A +/-50A, the thickness of the upper ITO layer and the lower ITO layer is the same, and the thickness of the Ag film is controlled to be 1000A +/-500A;
the preparation method of the substrate 1 comprises the following steps: firstly plating an ITO layer on a substrate, then plating an Ag layer, and finally plating an ITO layer.
Further, the process parameters of the ITO coating layer are selected as follows: DC sputtering power is 1000W + -200W, process pressure is 5.6mtorr + -0.5 mtorr, process gas is selected from Ar:20sccm +/-5 sccm 2 :2sccm +/-0.5 sccm; the upper and lower layers of ITO films have the same coating process.
The Ag film forming process parameters are selected as follows: DC sputtering power is 5000W +/-300W, process pressure is 5.6mtorr +/-0.5 mtorr, process gas is selected from Ar:20 sccm. + -.3 sccm.
The photoetching in the step 1) specifically comprises the following steps: selecting I-line wet etching glue as a mask, selecting 1000rpm +/-200 rpm as a gluing rotating speed, and controlling the glue thickness to be 2.5 microns +/-0.3 microns; the soft drying temperature is selected to be 90 +/-5 ℃, and the time is selected to be 60 +/-6 s; the exposure time is selected to be 350ms +/-50 ms, and the light intensity is selected to be 550mw/c square meter +/-50 mw/c square meter; the developing time is 60s +/-15 s, the developing solution is TMAH solution with the concentration of 2.38%, and the curing temperature is 120 +/-10 ℃.
In the step 2), wet etching is carried out, etching liquid adopts mixed nitrating acid which is mixed acid of nitric acid, phosphoric acid and acetic acid and is a commercially available product, and the upper ITO + Ag film etching is completed by using the mixed nitrating acid.
In the step 2), the etching rate of the nitrated mixed acid to ITO is 5A/s, the etching rate of the nitrated mixed acid to Ag is 250A/s, the selection ratio is high, the etching time of the upper layer ITO + Ag is controlled within 12-36s, the etching of the upper layer ITO + Ag can be completed, and the lowermost ITO is not etched on the substrate (the over-etching can be controlled to be less than 10A).
Further, in the step 3), the SiN film layer is deposited by adopting a CVD (chemical vapor deposition) mode to form a film, the SiN film layer is selected as the film layer, and the thickness is controlled to be 40nm +/-10 nm.
Specifically, the CVD film forming process parameters in the step 3): the power is 800W +/-50W, the pressure is 1000mT +/-10 mT, the temperature is 70 ℃ +/-5 ℃, and the gas is NH 3 The flow rate is 240sccm + -15 sccm, the film forming time is controlled within 16s + -2s, and the SiN film thickness can be controlled within 40nm + -10 nm.
In the step 4), dry etching is adopted for etching back etching process, siN is reserved on the side wall of the anode after back etching, and the surface of the anode and the channel are free of SiN residues;
specifically, the dry etching process comprises the following steps of: the power source power is 200W +/-10W, the Bias power is 40W +/-5W, and the etching gas is CF 4 The flow is 20sccm plus or minus 5sccm, the pressure is 10mT plus or minus 3mT, the temperature is 25 ℃ plus or minus 5 ℃, and the time is 20s plus or minus 3s, so that the SiN on the surface of the anode and the channel can be completely etched, and the SiN on the side wall of the anode is ensured to be reserved.
CF 4 The gas dry etching only etches SiN and does not damage ITO and Ag layers excessively.
In the step 5), carrying out ITO wet etching on the substrate 5, wherein the nitrated mixed acid is a mixed acid of nitric acid, phosphoric acid and acetic acid and is a commercially available product, and etching the lower layer of ITO is completed; wet etching is carried out at 25 +/-5 ℃ for 11-31s;
when the nitrified mixed acid is used for etching the bottom ITO, the SiN is protected on the side wall of the Ag, and the nitrified mixed acid does not etch the SiN, so that the Ag layer is not etched in the process of etching the bottom ITO.
Further, in the step 5), the photoresist is removed by a wet method, the photoresist removing liquid is NMP, and the photoresist is removed by spraying and soaking for 200s or 600s. The temperature was selected to be 50 ℃. + -. 5 ℃. The photoresist can be removed.
The SiN on the side wall can not be removed, and the performance of a product device is not influenced.
Further, the side wall SiN is selectively removed, and the removal mode adopts dry etching: the power source power is selected to be 600W +/-20W, the Bias power is selected to be 15W +/-2W, and the etching gas is selected to be CF 4 The flow rate is 50sccm +/-5 sccm 3 The flow is 10sccm +/-2 sccm, the pressure is 10mT +/-3 mT, the temperature is 25 +/-3 ℃, and the time is 20s +/-3 s, so that the etching of the side wall SiN can be completed without damaging the anode part.
Compared with the prior art, the substrate 6 finishes the side wall protection, when the lower layer ITO is etched, the side etching to Ag is avoided, the CD loss can be smaller than 0.1 mu m, the etching precision can be controlled, and the target pattern can be obtained.
Drawings
Fig. 1 is a schematic structural view of a substrate 1;
fig. 2 is a schematic structural view of the substrate 2;
FIG. 3 is a schematic structural diagram of a substrate 3;
fig. 4 is a schematic structural view of the substrate 4;
fig. 5 is a schematic structural view of the substrate 5;
FIG. 6 is a schematic view of a substrate 6;
FIG. 7 is a schematic diagram of a prior art etch;
FIG. 8 is an SEM photograph of the product of example 1;
FIG. 9 is an SEM photograph of a product of comparative example 1;
in the figure, 1-Ag layer, 2-upper ITO layer and 3-lower ITO layer; a 4-PR layer; 5-SiN layer.
Detailed Description
Example 1
A method for protecting and etching the side wall of an anode of a silicon-based Micro OLED Micro-display device comprises the following steps:
1) Firstly plating an ITO layer on a substrate, then plating an Ag layer, and finally plating an ITO layer; the film layer structure is made of ITO + Ag + ITO, the thickness of the upper and lower ITO films is controlled to be 100AControlling the thickness of the Ag film to be 1000A to obtain a substrate 1; the specific coating process parameters are as follows: firstly, plating a lower layer ITO film on a substrate, wherein the DC sputtering power is 1000W, the process pressure is 5.6mtorr, and the process gas is selected from Ar:20sccm, O 2 :2sccm; plating Ag film, and selecting the following technological parameters: DC sputtering power is 5000W, process pressure is 5.6mtorr, process gas is selected from Ar:20sccm, ag film thickness is controlled at 1000A; finally, an upper ITO film is plated, the plating process is the same as that of the lower ITO film, and the thickness is also 100A; obtaining a substrate 1, the structure schematic diagram is shown in fig. 1;
photoetching the substrate 1 coated with the ITO + Ag + ITO of the anode structure to perform anode graphical definition, selecting I-line wet etching glue as a mask, selecting 1100rpm as a glue coating rotating speed, and controlling the glue thickness to be 2.6 mu m; the soft drying temperature is selected to be 90 ℃, and the time is selected to be 65s; the exposure time is selected to be 320ms, and the light intensity is selected to be 550mw/c square meter; the developing time is selected to be 60s, TMAH solution with the concentration of 2.38% is selected as the developing solution, and the curing temperature is selected to be 120 ℃ to obtain the substrate 2; the structure of the substrate 2 is schematically shown in fig. 2;
2) Wet etching of the upper ITO and Ag layer is carried out on the substrate 2, etching liquid is a commercially available product and is selected from nitrated mixed acid (nitric acid, phosphoric acid and acetic acid), etching is carried out for 24s, etching of the upper ITO + Ag film is completed, and a substrate 3 is obtained, wherein the structural schematic diagram is shown in FIG. 3;
3) The substrate 3 adopts a CVD mode to deposit the SiN film layer, and the CVD film forming technological parameters are as follows: the power is 780W, the pressure is 1000mT, the temperature is 70 ℃, and the gas is NH 3 The flow rate is 250sccm, the film forming time is controlled at 18s, and the SiN film thickness is controlled at 40nm, so that a substrate 4 is obtained, wherein the structural schematic diagram is shown in FIG. 4;
4) And etching the substrate 4 by adopting a dry etching process to perform etching back, wherein the dry etching process is selected, and the power is selected: source power selection 210W, bias power selection 40W, etch gas selection CF 4 The flow is 22sccm, the pressure is 8mT, the temperature is 25 ℃, the time is 20s, siN is reserved on the side wall of the anode after back etching, and the surface of the anode and the channel have no SiN residue; obtaining a substrate 5, the schematic structural diagram of which is shown in fig. 5;
5) Carrying out ITO wet etching on the substrate 5, selecting nitrifying mixed acid (nitric acid, phosphoric acid and acetic acid) as an etching solution, and etching at 25 ℃ for 21s, completing etching of the lower layer ITO; removing the side wall SiN in a dry etching mode: the power source power is selected to be 600W, the Bias power is selected to be 15W, and the etching gas is selected to be CF 4 Flow rate of 50sccm, CHF 3 The flow is 10sccm plus or minus 2sccm, the pressure is 10mT, the temperature is 25 ℃, and the time is 20s, so that the etching of the side wall SiN can be completed without damaging the anode part. Removing the photoresist by adopting a wet method, wherein NMP is selected as a photoresist removing liquid, and spraying is adopted for 200s; and (3) obtaining a substrate 6, namely completing the process, wherein a schematic diagram is shown in FIG. 6, the substrate 5 completes the side wall protection, when the lower layer ITO is etched in the step 5), the lateral etching to Ag is avoided, the CD loss is 0.09 mu m, and an SEM image of a product is shown in FIG. 8.
Comparative example 1
A method for etching a silicon-based Micro OLED Micro-display device comprises the following steps:
1) Firstly plating an ITO layer on a substrate, then plating an Ag layer, and finally plating an ITO layer; selecting ITO + Ag + ITO as a film layer structure, controlling the thickness of the ITO films at 100A and the Ag films at 1000A to obtain a substrate 1; photoetching the substrate 1 coated with the ITO + Ag + ITO of the anode structure to perform anode graphical definition to obtain a substrate 2, wherein the specific preparation method is the same as the step 1) in the embodiment 1;
2) And (2) performing wet etching on the substrate 2, wherein etching liquid is a commercially available product which is mixed nitrating acid (nitric acid, phosphoric acid and acetic acid) selected, the etching time is 44s, the schematic diagram of the etched product is shown in FIG. 7, the SEM image of the etched product is shown in FIG. 9, and the CD loss is 1.1 μm.
Claims (7)
1. A method for protecting and etching the side wall of an anode of a silicon-based Micro OLED Micro-display device is characterized by comprising the following steps:
1) Photoetching the substrate 1 with the anode structure coated with ITO + Ag + ITO to perform anode graphical definition, and selecting photoresist as a mask to obtain a substrate 2;
2) Carrying out wet etching on the upper ITO and Ag layer of the substrate 2, wherein the etching time is controlled to be 12-36s;
obtaining a substrate 3;
3) The substrate 3 is deposited with a SiN film layer to obtain a substrate 4;
4) Etching the substrate 4 by adopting a dry etching back etching process, and reserving the SiN film layer on the side wall of the anode to obtain a substrate 5;
5) Carrying out wet etching on the lower layer of ITO on the substrate 5, and then removing the SiN film layer and the photoresist on the side wall of the anode to obtain a substrate 6;
in the step 3), the substrate 3 is deposited with the SiN film layer, CVD is adopted for film forming, and the process parameters are as follows: the power is 800W +/-50W, the pressure is 1000 mtorr +/-10 mtorr, the temperature is 70 +/-5 ℃, and the gas is NH 3 The flow rate is 240sccm + -15 sccm, the film forming time is controlled to be 16s + -2s, the SiN film thickness is controlled to be 40nm + -10 nm
In the step 4), a dry etching method is adopted for etching the back etching process, and the dry etching process comprises the following steps: the power source power is 200W +/-10W, the Bias power is 40W +/-5W, and the etching gas is CF 4 The flow is 20sccm +/-5 sccm, the pressure is 10 mtorr +/-3 mtorr, the temperature is 25 +/-5 ℃, and the time is 20s +/-3 s;
after etching, the CD loss is less than 0.1 μm.
2. The method according to claim 1, wherein in step 1), the substrate 1: the film structure is made of ITO + Ag + ITO, the thicknesses of the upper and lower layers of ITO film are controlled to be 100A +/-50A and are the same, and the thickness of the Ag film is controlled to be 1000A +/-500A.
3. The method according to claim 1, characterized in that the method for preparing the substrate 1: firstly plating an ITO layer on a substrate, then plating an Ag layer, and finally plating an ITO layer.
4. The method according to claim 3, wherein the ITO coating process parameters are selected from the group consisting of: DC sputtering power is 1000W + -200W, process pressure is 5.6mtorr + -0.5 mtorr, process gas is selected from Ar and O 2 Ar flow rate is 20sccm +/-5sccm 2 The flow rate is 2sccm +/-0.5 sccm; the upper and lower layers of ITO films have the same coating process.
5. The method according to claim 3 or 4, wherein the Ag film forming process parameters are selected as follows: the DC sputtering power is 5000W + -300W, the process pressure is 5.6mtorr + -0.5 mtorr, the process gas is Ar, and the Ar flow rate is 20sccm + -3 sccm.
6. The method according to claim 3, characterized in that the lithography in step 1) is in particular: selecting I-line wet etching glue for a mask, selecting 1000rpm +/-200 rpm for gluing, controlling the glue thickness to be 2.5 mu m +/-0.3 mu m, selecting 90 ℃ +/-5 ℃ for soft drying, selecting 60s +/-6 s for time, selecting 350ms +/-50 ms for exposure time, selecting 550mW/c square meter +/-50 mW/c square meter for light intensity, selecting 60s +/-15 s for developing time, selecting 2.38% TMAH solution for developing solution by mass concentration, and selecting 120 ℃ +/-10 ℃ for curing temperature.
7. The method according to claim 1 or 4, characterized in that in step 5), the sidewall SiN is removed after wet etching of the lower ITO layer, and the removal mode is dry etching: the power source power is selected to be 600W +/-20W, the Bias power is selected to be 15W +/-2W, and the etching gas is selected to be CF 4 And CHF 3 ，CF 4 The flow rate is 50sccm +/-5 sccm, CHF 3 The flow rate is 10sccm + -2 sccm, the pressure is 10 mtorr + -3 mtorr, the temperature is 25 deg.C + -3 deg.C, and the time is 20s + -3 s.
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