COB glue-free glass copper-clad plate, preparation method and application thereof

Abstract

This invention provides a COB (Copper Clad Glass) without adhesive, its preparation method, and its application, relating to the field of COB packaging materials technology. The preparation method of the COB without adhesive glass provided by this invention includes the following steps: (1) injecting metal elements into the surface of a glass substrate using high-energy ion beam technology to obtain a pretreated glass substrate; (2) depositing a transition layer on the surface of the pretreated glass substrate using high-power pulsed magnetron sputtering technology; the transition layer comprises one or more of Cu, Ni, and Cr; (3) preparing a copper layer on the surface of the transition layer using alternating high-power pulsed magnetron sputtering technology and high-power pulsed bias technology; (4) depositing a solder layer on the surface of the copper layer using ion beam technology to obtain the COB without adhesive glass. This invention can prepare a COB without adhesive glass with good light transmittance, good heat dissipation, high bonding strength, and a large copper layer thickness.

Description

Technical Field

[0001] This invention relates to the field of COB packaging materials technology, specifically to a COB adhesive-free glass copper-clad laminate, its preparation method, and its application. Background Technology

[0002] As the LED application market matures, users are demanding higher stability and reliability from products, especially under the same conditions, requiring superior energy efficiency, lower power consumption, and more competitive pricing. COB (Chip-on-Board) packaging devices are gradually gaining market share and becoming the mainstream packaging structure. To address issues such as low luminous efficacy, significant light decay, and poor heat dissipation, using glass as the packaging substrate is currently a popular choice.

[0003] There are two existing methods for preparing glass encapsulation substrates. One is to prepare copper-clad glass using a lamination process. However, the hot-pressing process can cause the adhesive to change color and reduce light transmittance. Moreover, the presence of the adhesive can also reduce heat dissipation. The other method is to plate copper on the glass surface using magnetron sputtering. However, due to the poor adhesion and high internal stress of this technology, it is impossible to make the copper layer thickness exceed 2 micrometers. Summary of the Invention

[0004] The purpose of this invention is to provide a COB glue-free glass copper-clad laminate, its preparation method and application. This invention can prepare a COB glue-free glass copper-clad laminate with good light transmittance, good heat dissipation and high adhesion, and the copper layer thickness can be greater than 20μm.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing a COB (Copper Clad) glass substrate without adhesive, comprising the following steps:

[0007] (1) Metal elements are injected into the surface of a glass substrate using high-energy ion beam technology to obtain a pretreated glass substrate;

[0008] (2) A transition layer is deposited on the surface of the pretreated glass substrate using high-power pulsed magnetron sputtering technology; the transition layer comprises one or more of Cu, Ni and Cr.

[0009] (3) A copper layer is prepared on the surface of the transition layer by alternating high-power pulsed magnetron sputtering technology and high-power pulsed bias technology;

[0010] (4) An ion beam technique is used to deposit a welding layer on the surface of the copper layer to obtain a COB glue-free copper-clad glass.

[0011] Preferably, the process conditions for the high-energy ion beam technology in step (1) include: beam current intensity of 10–100 mA and energy of 10–50 keV; the implantation dose of the metal element is 1 × 10⁻⁶. 15 ~1×10 16 ions / cm 2 .

[0012] Preferably, the metallic element in step (1) includes one or more of Ni, Cr, Cu, Ti and Al.

[0013] Preferably, the light transmittance of the pretreated glass substrate in step (1) is above 92%.

[0014] Preferably, the process conditions used in the high-power pulsed magnetron sputtering technology in step (2) include: power of 1 to 5 kW and frequency of 10 to 500 Hz.

[0015] Preferably, the deposition time of the transition layer in step (2) is 3 to 10 minutes.

[0016] Preferably, the process conditions used in the high-power pulse bias technology in step (3) include: negative voltage of 5-10kV, frequency of 10-200Hz, pulse width of 5-10μs, and power of 1-5kW.

[0017] Preferably, in step (3), the time for depositing the copper layer using high-power pulsed magnetron sputtering technology is 10 to 40 minutes each time; and the time for depositing the copper layer using high-power pulsed bias technology is 20 to 60 seconds each time.

[0018] The present invention provides a COB glue-free glass copper-clad laminate prepared by the preparation method described in the above technical solution.

[0019] This invention provides the application of the COB glue-free glass copper-clad laminate described above in circuit boards.

[0020] This invention provides a method for preparing a COB (Copper Clad Glass) without adhesive. The method involves high-energy metal element implantation into a glass substrate, forming a hybrid structure between the substrate and the implanted metal atoms. This hybrid structure exhibits excellent adhesion to both the glass substrate and the subsequent copper layer, forming a Si-O-Me (Me = Ni, Cr, Cu, Ti, Al) layer, thereby enhancing the peel strength of the glass-clad copper laminate. This invention employs high-power pulsed magnetron sputtering technology to deposit a transition layer on the surface of the pretreated glass substrate. The shallow implantation effect produced by high-power pulsed magnetron sputtering not only allows for further mixing and doping of Si-O-Me, effectively improving the adhesion between the transition layer and the Si-O-Me hybrid layer, but also results in excellent adhesion between the transition layer and the copper layer, leading to excellent overall metal layer adhesion. In this invention, high-power pulsed magnetron sputtering deposits the copper layer with high efficiency and high uniformity. The cyclic preparation using high-power pulsed magnetron sputtering and high-power pulsed bias technology significantly releases internal stress in the coating, resulting in a dense and thick copper layer. This allows for one-step forming of the glass-clad copper laminate without environmental pollution.

[0021] This invention employs a glue-free process to prepare glass-clad copper-clad laminates, resulting in good light transmittance, excellent heat dissipation, and high adhesion between layers. The COB glue-free glass-clad copper-clad laminate prepared by this invention has a roughness of no more than 0.2, enabling the fabrication of fine circuitry. Attached Figure Description

[0022] Figure 1 This is a process flow diagram for the preparation of the COB glue-free copper-clad glass substrate of the present invention;

[0023] Figure 2 The surface morphology of the COB glue-free glass copper-clad laminate prepared in Example 1 is shown in the figure.

[0024] Figure 3 The image shows the cross-sectional morphology of the COB glue-free glass copper-clad laminate prepared in Example 1. Detailed Implementation

[0025] This invention provides a method for preparing a COB (Copper Clad) glass substrate without adhesive, comprising the following steps:

[0026] (1) Metal elements are injected into the surface of a glass substrate using high-energy ion beam technology to obtain a pretreated glass substrate;

[0027] (2) A transition layer is deposited on the surface of the pretreated glass substrate using high-power pulsed magnetron sputtering technology; the transition layer comprises one or more of Cu, Ni and Cr.

[0028] (3) A copper layer is prepared on the surface of the transition layer by alternating high-power pulsed magnetron sputtering technology and high-power pulsed bias technology;

[0029] (4) An ion beam technique is used to deposit a welding layer on the surface of the copper layer to obtain a COB glue-free copper-clad glass.

[0030] This invention employs high-energy ion beam technology to implant metal elements onto the surface of a glass substrate, resulting in a pretreated glass substrate. In this invention, the metal element preferably includes one or more of Ni, Cr, Cu, Ti, and Al. The process conditions for the high-energy ion beam technology in this invention include: a beam current intensity preferably of 10–100 mA, more preferably 20 mA; an energy preferably of 10–50 keV, more preferably 20 keV; and an implantation dose of the metal element preferably of 1 × 10⁻⁶. 15 ~1×10 16 ions / cm 2 More preferably 5×10 15 ions / cm 2 In this invention, after the metal element is injected into the surface of the glass substrate, it forms a high-energy bond with the surface of the glass substrate to form a Si-O-Me (Me = Ni, Cr, Cu, Ti, Al) mixed layer, which is beneficial to improving the bonding force between the glass substrate and the transition layer and copper layer.

[0031] In this invention, the transmittance of the pretreated glass substrate is preferably above 92%.

[0032] After obtaining the pretreated glass substrate, this invention employs high-power pulsed magnetron sputtering technology to deposit a transition layer on the surface of the pretreated glass substrate. In this invention, the transition layer comprises one or more of Cu, Ni, and Cr. In this invention, the target material used for the high-power pulsed magnetron sputtering preferably comprises Cu, Ni, Cr, or a mixed alloy of any two of these metals in any proportion.

[0033] In this invention, the process conditions used in the high-power pulsed magnetron sputtering technology include: the power is preferably 1 to 5 kW, more preferably 3 kW; the frequency is preferably 10 to 500 Hz, more preferably 120 Hz; and the argon flow rate is preferably 100 to 150 sccm, more preferably 130 sccm.

[0034] In this invention, the deposition time of the transition layer is preferably 3 to 10 minutes, more preferably 5 minutes. In this invention, the thickness of the transition layer is preferably 10 to 100 nm, more preferably 9 to 15 nm.

[0035] After depositing a transition layer on the surface of the pretreated glass substrate, this invention alternately employs high-power pulsed magnetron sputtering and high-power pulsed bias techniques to prepare a copper layer on the surface of the transition layer. In this invention, the process conditions for the high-power pulsed magnetron sputtering technique include: a power preferably of 1–5 kW, more preferably 2–4 kW; a frequency preferably of 10–500 Hz, more preferably 100 Hz; and an argon flow rate preferably of 100–150 sccm, more preferably 120 sccm. In this invention, the target material used for the high-power pulsed magnetron sputtering is copper. In this invention, the process conditions for the high-power pulsed bias technique include: a negative voltage preferably of 5–10 kV, more preferably 6 kV; a frequency preferably of 10–200 Hz, more preferably 100 Hz; a pulse width preferably of 5–10 μs, more preferably 6 μs; a power preferably of 1–5 kW, more preferably 4 kW; and an argon flow rate preferably of 100–150 sccm, more preferably 120 sccm. In this invention, the target material used for the high-power bias is copper.

[0036] In this invention, the time for depositing a copper layer using high-power pulsed magnetron sputtering technology each time is preferably 10–40 min, more preferably 20–40 min; the thickness of the copper layer deposited using high-power pulsed magnetron sputtering technology each time is preferably 1–5 μm, more preferably 3–4 μm. In this invention, the time for depositing a copper layer using high-power pulsed bias technology each time is preferably 20–60 s, more preferably 30 s; the thickness of the copper layer deposited using high-power pulsed bias technology each time is preferably 20–50 nm.

[0037] In this invention, the copper layer prepared by the high-power pulsed bias technology is an internal stress relief layer. After depositing a transition layer on the surface of the pretreated glass substrate, this invention preferably first uses high-power pulsed magnetron sputtering technology to prepare a copper layer on the surface of the transition layer, and then uses high-power pulsed bias technology to prepare the internal stress relief layer; this process is repeated alternately, and finally, high-power pulsed magnetron sputtering technology is used to prepare the copper layer. The transition layer and the subsequent solder layer deposited on the surface of the copper layer are in contact with the copper layer prepared by the high-power pulsed magnetron sputtering technology.

[0038] In this invention, the total thickness of the copper layer is preferably 6 to 15 μm, more preferably 12 μm.

[0039] After obtaining the copper layer, this invention uses ion beam technology to deposit a solder layer on the surface of the copper layer to obtain a COB (Copper Clad Glass) without adhesive. In this invention, the composition of the solder layer preferably includes one or more of tin and zinc. The process conditions used in this invention for the ion beam technology include: the target material preferably includes one or more of tin and zinc; the argon flow rate is preferably 100–150 sccm, more preferably 120 sccm; and the power is preferably 1–4 kW, more preferably 2 kW. In this invention, the deposition time of the solder layer is preferably 5–15 min, more preferably 10 min. In this invention, the thickness of the solder layer is preferably 200–500 nm.

[0040] This invention provides a COB (Copper Clad Glass) laminate prepared by the preparation method described above. In this invention, the COB laminate includes a pretreated glass substrate and a transition layer, a copper layer, and a welding layer sequentially stacked on the surface of the pretreated glass substrate; the pretreated glass substrate is a glass substrate doped with metal elements.

[0041] In this invention, the light transmittance of the COB glue-free copper-clad glass is preferably above 92%.

[0042] This invention provides the application of the COB glue-free glass copper-clad laminate described above in circuit boards.

[0043] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0044] Example 1

[0045] according to Figure 1 The process shown is used to prepare COB (Copper Clad) glass without adhesive:

[0046] S1: Ni metal element is implanted into the surface of a glass substrate using high-energy ion beam technology, forming high-energy bonds with the glass substrate surface to obtain a pretreated glass substrate. The beam current intensity is 20 mA, the energy is 20 keV, and the implantation dose is 5 × 10⁻⁶. 15 ions / cm 2 .

[0047] S2: A transition layer is deposited on the surface of the pretreated glass substrate by high-power pulsed magnetron sputtering technology. The selected target material is a Ni-Cr (Ni and Cr atomic ratio is 2:8) mixed alloy, the argon flow rate is 130 sccm, the power is 3 kW, the frequency is 120 Hz, the deposition time is 5 min, and a transition layer with a thickness of 15 nm is obtained.

[0048] S3: A copper layer was deposited using high-power pulsed magnetron sputtering technology. The target material was copper, the argon flow rate was 120 sccm, the power was 4 kW, the frequency was 100 Hz, and the deposition time was 40 min, resulting in a copper layer with a thickness of 4 μm.

[0049] S4: Cu was deposited using high-power pulsed bias technology. The target material was Cu, the negative voltage was 6kV, the pulse width was 6μs, the argon flow rate was 120sccm, the power was 4kW, the frequency was 100Hz, and the deposition time was 30s, resulting in a copper layer (stress relief layer) with a thickness of 20nm.

[0050] S5: Repeat steps S3 and S4 until the total thickness of the copper layer is 12μm;

[0051] S6: A tin solder layer is deposited on the surface of the copper layer using ion beam technology. The selected target material is tin, the argon flow rate is 120 sccm, the power is 2 kW, the deposition time is 10 min, and a tin solder layer with a thickness of 200 nm is obtained.

[0052] Example 2

[0053] according to Figure 1 The process shown is used to prepare COB (Copper Clad) glass without adhesive:

[0054] S1: Ni metal element is implanted into the surface of a glass substrate using high-energy ion beam technology, forming high-energy bonds with the glass substrate surface to obtain a pretreated glass substrate. The beam current intensity is 10 mA, the energy is 10 keV, and the implantation dose is 5 × 10⁻⁶. 15 ions / cm 2 .

[0055] S2: A transition layer was deposited on the surface of the pretreated glass substrate using high-power pulsed magnetron sputtering technology. The selected target material was a Ni-Cr (Ni and Cr atomic ratio of 2:8) mixed alloy, the argon flow rate was 130 sccm, the power was 3 kW, the frequency was 120 Hz, the deposition time was 3 min, and a transition layer with a thickness of 9 nm was obtained.

[0056] S3: A copper layer was deposited using high-power pulsed magnetron sputtering technology. The target material was copper, the argon flow rate was 120 sccm, the power was 4 kW, the frequency was 100 Hz, and the deposition time was 40 min, resulting in a copper layer with a thickness of 4 μm.

[0057] S4: Cu was deposited using high-power pulsed bias technology. The target material was Cu, the negative voltage was 6kV, the pulse width was 6μs, the argon flow rate was 120sccm, the power was 4kW, the frequency was 100Hz, and the deposition time was 30s, resulting in a copper layer (stress relief layer) with a thickness of 20nm.

[0058] S5: Repeat steps S3 and S4 until the total thickness of the copper layer is 12μm;

[0059] S6: A tin solder layer is deposited on the surface of the copper layer using ion beam technology. The selected target material is tin, the argon flow rate is 120 sccm, the power is 2 kW, the deposition time is 10 min, and a tin solder layer with a thickness of 200 nm is obtained.

[0060] Example 3

[0061] according to Figure 1 The process shown is used to prepare COB (Copper Clad) glass without adhesive:

[0062] S1: Ni metal element is implanted into the surface of a glass substrate using high-energy ion beam technology, forming high-energy bonds with the glass substrate surface to obtain a pretreated glass substrate. The beam current intensity is 20 mA, the energy is 20 keV, and the implantation dose is 5 × 10⁻⁶. 15 ions / cm 2 .

[0063] S2: A transition layer is deposited on the surface of the pretreated glass substrate by high-power pulsed magnetron sputtering technology. The selected target material is a Ni-Cr (Ni and Cr atomic ratio is 2:8) mixed alloy, the argon flow rate is 130 sccm, the power is 3 kW, the frequency is 120 Hz, the deposition time is 5 min, and a transition layer with a thickness of 15 nm is obtained.

[0064] S3: A copper layer was deposited using high-power pulsed magnetron sputtering technology. The target material was copper, the argon flow rate was 150 sccm, the power was 2 kW, the frequency was 100 Hz, and the deposition time was 40 min, resulting in a copper layer with a thickness of 3 μm.

[0065] S4: Cu was deposited using high-power pulsed bias technology. The target material was Cu, the negative voltage was 6kV, the pulse width was 6μs, the argon flow rate was 120sccm, the power was 4kW, the frequency was 100Hz, and the deposition time was 30s, resulting in a copper layer (stress relief layer) with a thickness of 20nm.

[0066] S5: Repeat steps S3 and S4 until the total thickness of the copper layer is 12μm;

[0067] S6: A tin solder layer is deposited on the surface of the copper layer using ion beam technology. The selected target material is tin, the argon flow rate is 120 sccm, the power is 2 kW, the deposition time is 10 min, and a tin solder layer with a thickness of 200 nm is obtained.

[0068] Comparative Example 1

[0069] S1: A transition layer was deposited on the surface of a glass substrate using high-power pulsed magnetron sputtering technology. The selected target material was a Ni-Cr (Ni to Cr atomic ratio of 2:8) mixed alloy. The argon flow rate was 130 sccm, the power was 3 kW, the frequency was 120 Hz, and the deposition time was 5 min, resulting in a transition layer with a thickness of 15 nm.

[0070] S2: A copper layer was deposited using high-power pulsed magnetron sputtering technology. The target material was copper, the argon flow rate was 120 sccm, the power was 4 kW, the frequency was 100 Hz, and the deposition time was 120 min, resulting in a copper layer with a thickness of 12 μm.

[0071] S3: A tin solder layer is deposited on the surface of the copper layer using ion beam technology. The selected target material is tin, the argon flow rate is 120 sccm, the power is 2 kW, the deposition time is 10 min, and a tin solder layer with a thickness of 200 nm is obtained.

[0072] Comparative Example 2

[0073] S1: Ni metal element is implanted into the surface of a glass substrate using high-energy ion beam technology, forming high-energy bonds with the glass substrate surface to obtain a pretreated glass substrate. The beam current intensity is 20 mA, the energy is 20 keV, and the implantation dose is 5 × 10⁻⁶. 15 ions / cm 2 .

[0074] S2: A transition layer is deposited on the surface of the pretreated glass substrate by high-power pulsed magnetron sputtering technology. The selected target material is a Ni-Cr (Ni and Cr atomic ratio is 2:8) mixed alloy, the argon flow rate is 130 sccm, the power is 3 kW, the frequency is 120 Hz, the deposition time is 5 min, and a transition layer with a thickness of 15 nm is obtained.

[0075] S3: A copper layer was deposited using high-power pulsed magnetron sputtering technology. The target material was copper, the argon flow rate was 120 sccm, the power was 4 kW, the frequency was 100 Hz, and the deposition time was 120 min, resulting in a copper layer with a thickness of 12 μm.

[0076] S4: A tin solder layer is deposited on the surface of the copper layer using ion beam technology. The selected target material is tin, the argon flow rate is 120 sccm, the power is 2 kW, the deposition time is 10 min, and a tin solder layer with a thickness of 200 nm is obtained.

[0077] Test case

[0078] The bonding strength of the glass-copper clad laminates prepared in Examples 1-3 and Comparative Examples 1-2 is shown in Table 1:

[0079] Table 1. Adhesion strength of the glass-coated copper sheets prepared in Examples 1-3 and Comparative Examples 1-2

[0080]

[0081] The surface and cross-sectional morphology of the COB glue-free glass copper-clad laminate prepared in Example 1 are as follows: Figures 2-3 As shown. By Figures 2-3 It can be seen that the surface of the COB glue-free glass copper-clad laminate is highly dense, with few particles and pores and low roughness; the cross-section exhibits a multi-layer morphology, with high cross-section density and no columnar crystal formation.

[0082] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a COB (Copper Clad) glass substrate without adhesive, comprising the following steps: (1) Metal elements are injected into the surface of a glass substrate using high-energy ion beam technology to obtain a pretreated glass substrate; (2) A transition layer is deposited on the surface of the pretreated glass substrate using high-power pulsed magnetron sputtering technology; the transition layer comprises one or more of Cu, Ni and Cr. (3) A copper layer is prepared on the surface of the transition layer by alternating high-power pulsed magnetron sputtering technology and high-power pulsed bias technology; (4) An ion beam technique is used to deposit a welding layer on the surface of the copper layer to obtain a COB glue-free copper-clad glass.

2. The production method according to claim 1, characterized by, The process conditions of the high-energy ion beam technology in step (1) include: beam intensity of 10-100 mA, energy of 10-50 keV; the implantation dose of the metal element is 1x1014-1x1016ions / cm2. 15 16 2 ions / cm 2 .

3. The production method according to claim 1 or 2, characterized by, The metallic element mentioned in step (1) includes one or more of Ni, Cr, Cu, Ti and Al.

4. The method of claim 1, wherein, The light transmittance of the pretreated glass substrate in step (1) is above 92%.

5. The preparation method according to claim 1, characterized in that, The process conditions used in step (2) of the high-power pulsed magnetron sputtering technology include: power of 1 to 5 kW and frequency of 10 to 500 Hz.

6. The preparation method according to claim 1, characterized in that, The deposition time of the transition layer in step (2) is 3 to 10 minutes.

7. The preparation method according to claim 1, characterized in that, The process conditions used in the high-power pulse bias technology described in step (3) include: negative voltage of 5-10kV, frequency of 10-200Hz, pulse width of 5-10μs, and power of 1-5kW.

8. The preparation method according to claim 1, characterized in that, In step (3), the time for depositing the copper layer using high-power pulsed magnetron sputtering technology is 10 to 40 minutes each time; the time for depositing the copper layer using high-power pulsed bias technology is 20 to 60 seconds each time.

9. The COB glue-free glass copper-clad laminate prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the COB glue-free glass copper-clad laminate of claim 9 in circuit boards.

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