ESD protection composite structure, ESD protection device, and manufacturing method thereof
11044798 · 2021-06-22
Assignee
Inventors
- Ding-Shiang Wang (Tainan, TW)
- Jia-Jen Chang (Yunlin County, TW)
- Ming-Sheng Leu (Hsinchu County, TW)
- Tai-Sheng Chen (Kaohsiung, TW)
- Chin-Te Shih (Hsinchu County, TW)
Cpc classification
C23C14/024
CHEMISTRY; METALLURGY
H01L21/67323
ELECTRICITY
H01L21/67396
ELECTRICITY
H01L21/67366
ELECTRICITY
C23C14/022
CHEMISTRY; METALLURGY
B65G47/74
PERFORMING OPERATIONS; TRANSPORTING
H01L21/67306
ELECTRICITY
H01L21/6733
ELECTRICITY
International classification
C23C14/32
CHEMISTRY; METALLURGY
B65G47/74
PERFORMING OPERATIONS; TRANSPORTING
C23C14/00
CHEMISTRY; METALLURGY
Abstract
An ESD protection composite structure includes a link layer, a progressive layer, and a composite layer. The link layer is used for disposing the ESD protection composite structure on a substrate, wherein a material of the link layer includes a metal material. The progressive layer is disposed on the link layer, wherein the material of the progressive layer includes a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate in a thickness direction of the progressive layer. The composite layer is disposed on the progressive layer, wherein the composite layer includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer may make a sheet resistance value of the composite layer 1×10.sup.7 Ω/sq to 1×10.sup.8 Ω/sq.
Claims
1. An ESD protection composite structure, comprising: a link layer used for disposing the ESD protection composite structure on a substrate, wherein a material of the link layer comprises a metal material; a progressive layer disposed on the link layer, wherein a material of the progressive layer comprises a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate in a thickness direction of the progressive layer; and a composite layer disposed on the progressive layer, wherein the composite layer comprises a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer may make a sheet resistance value of the composite layer 1×10.sup.7 Ω/sq to 1×10.sup.8 Ω/sq.
2. The ESD protection composite structure of claim 1, wherein metals in the metal material, the stoichiometric metal oxide material, and the non-stoichiometric metal oxide material are the same.
3. The ESD protection composite structure of claim 1, wherein a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer is 0.005:1 to 0.01:1.
4. The ESD protection composite structure of claim 1, wherein the metal material comprises Ti, Al, Cu, Ni, Cr, Ta, or V, the non-stoichiometric metal oxide material comprises TiOx, AlOx, CuOx, NiOx, CrOx, TaOx, or VOx, and 0<x<a stoichiometry of a metal oxide, and the stoichiometric metal oxide material comprises TiO.sub.2, Al.sub.2O.sub.3, CuO, NiO, Cr.sub.2O.sub.3, Ta.sub.2O.sub.5, or V.sub.2O.sub.5.
5. The ESD protection composite structure of claim 1, wherein the metal material is Ti, the non-stoichiometric metal oxide material is TiOx, the stoichiometric metal oxide material is TiO.sub.2, and x in TiOx in the progressive layer is 0<x<1.5 and x in TiOx in the composite layer is 1.5<x<2.
6. The ESD protection composite structure of claim 1, wherein a thickness of the ESD protection composite structure is 105 nm to 3000 nm.
7. The ESD protection composite structure of claim 1, wherein the ESD protection composite structure has a hardness of 8 GPa to 12 GPa, a pencil hardness of 5 to 7, an adhesion of 8 N to 12 N, and a temperature resistance of a room temperature to 500° C.
8. An ESD protection device, comprising: a substrate; and the ESD protection composite structure of claim 1 disposed on the substrate via a link layer.
9. The ESD protection device of claim 8, wherein a material of the substrate comprises a metal material, a ceramic material, a resin material, or a combination of the materials.
10. The ESD protection device of claim 9, wherein the metal material comprises stainless steel or aluminum, the ceramic material comprises TiO.sub.2, Al.sub.2O.sub.3, CuO, NiO, Cr.sub.2O.sub.3, Ta.sub.2O.sub.5, or V.sub.2O.sub.5, and the resin material comprises polycarbonate, epoxy resin, polyvinyl chloride, polypropylene, or polyethylene terephthalate.
11. The ESD protection device of claim 8, wherein a surface of the substrate has a surface treatment layer, and the link layer is formed on the surface treatment layer.
12. The ESD protection device of claim 8, wherein metals in the metal material, the stoichiometric metal oxide material, and the non-stoichiometric metal oxide material are the same.
13. The ESD protection device of claim 8, wherein a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material in the composite layer is 0.005:1 to 0.01:1.
14. The ESD protection device of claim 8, wherein the metal material comprises Ti, Al, Cu, Ni, Cr, Ta, or V, the non-stoichiometric metal oxide material comprises TiOx, AlOx, CuOx, NiOx, CrOx, TaOx, or VOx, and 0<x<a stoichiometry of a metal oxide, and the stoichiometric metal oxide material comprises TiO.sub.2, Al.sub.2O.sub.3, CuO, NiO, Cr.sub.2O.sub.3, Ta.sub.2O.sub.5, or V.sub.2O.sub.5.
15. The ESD protection device of claim 8, wherein a material of the substrate is aluminum or stainless steel, the metal material is Ti, the non-stoichiometric metal oxide material is TiOx, the stoichiometric metal oxide material is TiO.sub.2, and x in TiOx in the progressive layer is 0<x<1.5 and x in TiOx in the composite layer is 1.5<x<2.
16. The ESD protection device of claim 8, wherein a thickness of the ESD protection composite structure is 105 nm to 3000 nm.
17. The ESD protection device of claim 8, wherein the ESD protection composite structure has a hardness of 8 GPa to 12 GPa, a pencil hardness of 5 to 7, an adhesion of 8 N to 12 N, and a temperature resistance of a room temperature to 500° C.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The accompanying drawings are included to provide further understanding, and are incorporated in and constitute a part of this specification. The drawings illustrate exemplary embodiments and, together with the description, serve to explain the principles of the disclosure.
(2)
(3)
(4)
DETAILED DESCRIPTION OF DISCLOSED EMBODIMENTS
(5)
(6) Referring to
(7) In some exemplary embodiments, the surface treatment 200 includes, for instance, disposing the substrate 100 in an arc ion plating apparatus, and performing surface treatment on the substrate 100 using oxygen/argon as a plasma to form the surface treatment layer 102 on the surface of the substrate 100. In some embodiments, the material of the substrate 100 is, for instance, aluminum or stainless steel, the ratio of oxygen/argon is, for instance, 0.5:1 to 1:0.5, the process bias is, for instance, 500 V to 900 V, and in some exemplary embodiments, the ratio of oxygen/argon is, for instance, 0.65:1 to 0.85:1, and the process bias is, for instance, 600 V to 800 V.
(8) Next, referring to
(9) In some exemplary embodiments, the forming of the link layer 110 includes, for instance, using the arc ion plating apparatus of the exemplary embodiment of
(10) Next, referring to
(11) In some exemplary embodiments, the forming of the progressive layer 120 includes, for instance, using the arc ion plating apparatus of the exemplary embodiment of
(12) Next, referring to
(13) The reason that the material of the composite layer 130 includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material is that the sheet resistance value of the stoichiometric metal oxide material is too high (about 1×10.sup.12 Ω/sq in the case of TiO.sub.2) such that the issue of being unsuitable for ESD protection application exists, and therefore in the disclosure, by mixing a non-stoichiometric metal oxide material of a specific ratio in the stoichiometric metal oxide material, the sheet resistance value of the composite layer 130 may be 1×10.sup.7 f′/sq to 1×10.sup.8 Ω/sq suitable for ESD protection application.
(14) In some exemplary embodiments, the forming of the composite layer 130 includes, for instance, using the arc ion plating apparatus of the exemplary embodiment of
(15) Via the manufacturing method recited in
(16) The ESD protection device 10 having the ESD protection composite structure 140 of the disclosure is described via
(17) The ESD protection device 10 of the disclosure includes an ESD protection composite structure 140 and a substrate 100. The ESD protection composite structure 140 includes a link layer 110, a progressive layer 120, and a composite layer 130. The link layer 110 is disposed on the surface treatment layer 102 of the substrate 100, wherein the material of the link layer 110 includes a metal material. The progressive layer 120 is disposed on the link layer 110, wherein the material of the progressive layer 120 includes a non-stoichiometric metal oxide material, and an oxygen concentration in the non-stoichiometric metal oxide material is increased gradually away from the substrate 100 in a thickness direction of the progressive layer 120. The composite layer 130 is disposed on the progressive layer 120, wherein the material of the composite layer 130 includes a stoichiometric metal oxide material and a non-stoichiometric metal oxide material, and a ratio of the non-stoichiometric metal oxide material and the stoichiometric metal oxide material may make a sheet resistance value of the composite layer 130 1×10.sup.7 Ω/sq to 1×10.sup.8 Ω/sq. In an embodiment, metals in the metal material, the stoichiometric metal oxide material, and the non-stoichiometric metal oxide material in the ESD protection composite structure 140 are the same. Moreover, in an embodiment, the ESD protection composite structure 140 has a hardness of, for instance, 8 GPa to 12 GPa, a pencil hardness of, 5 to 7, an adhesion of, for instance, 8 N to 12N, a temperature resistance of, for instance, room temperature to 500° C., and a thickness of, for instance, 105 nm to 3000 nm.
(18) In addition to the hardness, pencil hardness, adhesion, temperature resistance, and the thickness of the ESD protection composite structure 140, the material and specification of each member in the ESD protection device 10 are described in detail in the manufacturing method of
(19) It may be known from the manufacturing method and the resulting ESD protection device that, by performing the surface treatment 200 on the substrate 100 and then forming the link layer 110 on the substrate 100 after the surface treatment, the adhesion of the link layer 110 and the substrate 100 (surface treatment layer 102) may be increased. Moreover, by forming the progressive layer 120 between the composite layer 130 and the link layer 110, the composite layer 130 having a stoichiometric metal oxide as the main component may be adhered well to the link layer 110 having a metal as the main component via the progressive layer 120. As a result, the ESD protection composite structure 140 of the disclosure has good adhesion with the substrate 100 as a whole. In the case that the adhesion between the ESD protection composite structure 140 and the substrate 100 is good, since the ESD protection composite structure 140 is not readily peeled off, the ESD protection device 100 of the disclosure may also have high hardness and high pencil hardness.
(20) Moreover, based on the material (metal material, non-stoichiometric metal oxide material, and a mixture of stoichiometric metal oxide material and non-stoichiometric metal oxide material) of each layer of the ESD protection composite structure of the disclosure, the ESD protection composite structure of the disclosure as a whole may have high-temperature resistance properties. Moreover, since the material of the composite layer 130 of the topmost layer may obtain a sheet resistance value of 1×10.sup.7 Ω/sq to 1×10.sup.8 Ω/sq suitable for ESD protection application by mixing a non-stoichiometric metal oxide material of a specific ratio in the stoichiometric metal oxide material, good ESD protection properties may be obtained, and good acid and alkali corrosion resistance properties may be obtained based on the properties of the stoichiometric metal oxide material.
(21) Moreover, it may be known from the manufacturing method above that, all of the films of
Experimental Examples
(22) <Manufacture of ESD Protection Device>
(23) An arc ion plating apparatus was used to form a test piece of an ESD protection device having the ESD protection composite structure of the disclosure on a test substrate (experimental examples 1 to 4). The observation results of the resulting test pieces of experimental examples 1 to 4 show that the resulting films are complete and do not show signs of peeling. Moreover, the sheet resistance values obtained in a sheet resistance value test performed on the test pieces of experimental examples 1 to 4 are all in the range of 1×10.sup.7 Ω/sq to 1×10.sup.8 Ω/sq. The test results of experimental examples 1 to 4 are provided in Table 1.
(24) TABLE-US-00001 TABLE 1 Experimental Experimental Experimental Experimental example 1 example 2 example 3 example 4 Substrate Al Al Al Al Target Ti Ti Ti Ti Surface Plasma Oxygen/argon Oxygen/argon Oxygen/argon Oxygen/argon treatment Process 650 700 750 850 bias (V) Link layer Process 0.850 0.750 0.750 0.850 current density (A/cm.sup.2) Process 300 300 300 300 bias (V) Progressive Process 0.850 0.750 0.750 0.850 layer current density (A/cm.sup.2) Process 250 250 250 250 bias (V) Oxygen 60 60 80 80 flow Composite Process 0.750 0.650 0.650 0.650 layer current density (A/cm.sup.2) Process 100 100 100 100 bias (V) Oxygen 90 90 120 150 flow Thickness (nm) of 1800 1800 1800 1800 ESD protection composite structure Film integrity No peeling No peeling No peeling No peeling Sheet resistance 1 × 10.sup.7 to 1 × 10.sup.7 to 1 × 10.sup.7 to 1 × 10.sup.7 to value (Ω/sq) 1 × 10.sup.8 1 × 10.sup.8 1 × 10.sup.8 1 × 10.sup.8 Film integrity after No peeling No peeling No peeling No peeling temperature resistance test Sheet resistance 1 × 10.sup.7 to 1 × 10.sup.7 to 1 × 10.sup.7 to 1 × 10.sup.7 to value (Ω/sq) after 1 × 10.sup.8 1 × 10.sup.8 1 × 10.sup.8 1 × 10.sup.8 temperature resistance test Pencil hardness ≥6H ≥6H ≥6H ≥6H
(25) <Temperature Resistance Test and Electrical Property Test of ESD Protection Device>
(26)
(27) <Acid and Alkali Corrosion Resistance Test of ESD Protection Device>
(28) A 15 cm×15 cm 304 stainless steel was used as a substrate, and test pieces with thickness of 1500 nm and 2500 nm of an ESD protection composite structure were respectively manufactured. Next, a blank sheet (304 stainless steel substrate without an ESD protection composite structure), the 1500 nm test piece, and the 2500 nm test piece were respectively brought in contact with sulfuric acid (H.sub.2SO.sub.4) and potassium hydroxide (KOH), and then the current density of the blank piece and each test piece was measured. The measured results are shown in
(29) <Pencil Hardness Test of ESD Protection Device>
(30) A pencil hardness test was performed on the test pieces of experimental examples 1 to 4 using a pencil hardness tester. The test results show that, the pencil hardnesses of the test pieces of experimental examples 1 to 4 are all 6H or above, and therefore the ESD protection device of the disclosure has good hardness properties. Moreover, the test results of experimental examples 1 to 4 are provided in Table 1.
(31) Based on the above, the ESD protection composite structure of the disclosure has a composite structure formed by a link layer (metal material)/progressive layer (non-stoichiometric metal oxide material having an oxygen concentration varying with film thickness)/composite layer (for which a stoichiometric metal oxide material used as the main component is mixed with a non-stoichiometric metal oxide material and having a sheet resistance value suitable for ESD protection application). In particular, the ESD protection composite structure has good adhesion with the substrate as a whole via the link layer and the progressive layer, ESD protection properties and acid and alkali corrosion resistance properties are provided via the composite layer, high-temperature resistance properties are provided via each layer material of the ESD protection composite structure, and the ESD protection composite structure further has high hardness and high pencil hardness via good adhesion. Therefore, the ESD protection device having the ESD protection composite structure of the disclosure may have all of good ESD protection properties, high-temperature resistance, high mechanical properties (adhesion, hardness, and pencil hardness), and high acid and alkali corrosion resistance properties.
(32) Moreover, the ESD protection device of the disclosure may be completed using the same deposition equipment (arc ion plating apparatus) and using the same metal source (metal target). In particular, the progressive layer and composite layer having the properties of the disclosure may be formed by adjusting the flow of the reaction gas, and therefore the manufacturing method of the disclosure may be simplified. Moreover, since in the disclosure, a metal target is used as the common metal source of each layer in the ESD protection composite structure, the metal target is relatively cheap and having a large process area to facilitate industrialization. Therefore, in the disclosure, an ESD protection composite structure and an ESD protection device with all the good properties of the disclosure may be manufactured via a cheap and simple manufacturing method.
(33) It will be apparent to those skilled in the art that various modifications and variations may be made to the structure of the disclosed embodiments without departing from the scope or spirit of the disclosure. In view of the foregoing, it is intended that the disclosure cover modifications and variations of this disclosure provided they fall within the scope of the following claims and their equivalents.