Journal of Inorganic Materials ›› 2024, Vol. 39 ›› Issue (1): 17-31.DOI: 10.15541/jim20230345
• REVIEW • Previous Articles Next Articles
KE Xin1,2(
), XIE Bingqing1,2, WANG Zhong1,3(), ZHANG Jingguo1,3,4, WANG Jianwei1,3, LI Zhanrong1,3,4, HE Huijun1,3, WANG Limin1,3
Received:2023-08-01
Revised:2023-10-12
Published:2024-01-20
Online:2023-11-22
Contact:
WANG Zhong, professor. E-mail: wzwz99@126.comAbout author:KE Xin (1997-), male, PhD candidate. E-mail: kexin0308@qq.com
Supported by:CLC Number:
KE Xin, XIE Bingqing, WANG Zhong, ZHANG Jingguo, WANG Jianwei, LI Zhanrong, HE Huijun, WANG Limin. Progress of Interconnect Materials in the Third-generation Semiconductor and Their Low-temperature Sintering of Copper Nanoparticles[J]. Journal of Inorganic Materials, 2024, 39(1): 17-31.
Fig. 1 Global GDP and semiconductor market size in 2014-2020[7]
| Parameter | Si | GaAs | SiC | GaN | Diamond |
|---|---|---|---|---|---|
| Band gap/eV | 1.12 | 1.43 | 3.26 | 3.45 | 5.45 |
| Dielectric constant | 11.9 | 13.1 | 10.1 | 9 | 5.5 |
| Breakdown field/ (kV·cm-1) | 300 | 400 | 2200 | 2000 | 10000 |
| Electron mobility/(cm2·V-1·s-1) | 1500 | 8500 | 1000 | 1250 | 2200 |
| Hole mobility/ (cm2·V-1·s-1） | 600 | 400 | 115 | 850 | 850 |
| Thermal conductivity/ (W·cm-1·K-1) | 1.5 | 0.46 | 4.9 | 1.3 | 22 |
| Electron saturation drift velocity/(×107, cm·s-1) | 1 | 1 | 2 | 2.2 | 2.7 |
Table 1 Comparison on performance parameters of the main semiconductor material [10]
| Parameter | Si | GaAs | SiC | GaN | Diamond |
|---|---|---|---|---|---|
| Band gap/eV | 1.12 | 1.43 | 3.26 | 3.45 | 5.45 |
| Dielectric constant | 11.9 | 13.1 | 10.1 | 9 | 5.5 |
| Breakdown field/ (kV·cm-1) | 300 | 400 | 2200 | 2000 | 10000 |
| Electron mobility/(cm2·V-1·s-1) | 1500 | 8500 | 1000 | 1250 | 2200 |
| Hole mobility/ (cm2·V-1·s-1） | 600 | 400 | 115 | 850 | 850 |
| Thermal conductivity/ (W·cm-1·K-1) | 1.5 | 0.46 | 4.9 | 1.3 | 22 |
| Electron saturation drift velocity/(×107, cm·s-1) | 1 | 1 | 2 | 2.2 | 2.7 |
Fig. 2 Third-generation semiconductor applications
Fig. 3 Package interconnection structure of typical power semiconductor module[14]
Fig. 4 Applied temperature range and application possibilities of different package interconnect materials[22]
Fig. 5 Virtual equilibrium phase diagram for TLP bonding[32]
Fig. 6 Schematic diagram of TLP bonding principle[33]
| Material | Temperature/℃ | Relative market price* | Relative performance | ||
|---|---|---|---|---|---|
| Bonding | IMC | Thermal conductivity | Electrical conductivity | ||
| Cu-Sn | 280 | 415(Cu6Sn5) | Cu: 0.5 | Cu: 4.4 | Cu: 4.1 |
| 676(Cu3Sn) | Sn: 0.8 | ||||
| Ni-Sn | 300 | 800(Ni3Sn3) | Ni: 1 | Ni: 1 | Ni: 1 |
| Sn: 0.8 | |||||
| Au-Sn | 250 | 419(AuSn) | Au: 2600 | Au: 3.5 | Au: 3.1 |
| Sn: 0.8 | |||||
| Ag-Sn | 250 | 480(Ag3Sn) | Ag: 63 | Ag: 4.7 | Ag: 4.4 |
| Sn: 0.8 | |||||
| Ag-In | 200 | 495 | Ag: 63 | Ag: 4.7 | Ag: 4.7 |
| In: 37.5 | |||||
| Au-In | 175 | 880 | Au: 2600 | Au: 3.1 | Au: 3.1 |
| In: 37.5 | |||||
Table 2 Various TLP bonding materials and their properties[60]
| Material | Temperature/℃ | Relative market price* | Relative performance | ||
|---|---|---|---|---|---|
| Bonding | IMC | Thermal conductivity | Electrical conductivity | ||
| Cu-Sn | 280 | 415(Cu6Sn5) | Cu: 0.5 | Cu: 4.4 | Cu: 4.1 |
| 676(Cu3Sn) | Sn: 0.8 | ||||
| Ni-Sn | 300 | 800(Ni3Sn3) | Ni: 1 | Ni: 1 | Ni: 1 |
| Sn: 0.8 | |||||
| Au-Sn | 250 | 419(AuSn) | Au: 2600 | Au: 3.5 | Au: 3.1 |
| Sn: 0.8 | |||||
| Ag-Sn | 250 | 480(Ag3Sn) | Ag: 63 | Ag: 4.7 | Ag: 4.4 |
| Sn: 0.8 | |||||
| Ag-In | 200 | 495 | Ag: 63 | Ag: 4.7 | Ag: 4.7 |
| In: 37.5 | |||||
| Au-In | 175 | 880 | Au: 2600 | Au: 3.1 | Au: 3.1 |
| In: 37.5 | |||||
Fig. 7 Cu@Ag nanoparticles and performance characterization[85] (a, b) STEM images of Cu@Ag nanoparticles; (c) Schematic diagram of the filling effect of nanoparticles on silver conductive adhesive; (d) Influence of the conductive fillers’ percentages on the strength of the conductive adhesives; (e) Dependence of conductive fillers’ percentages on the strength and conductivity of conductive adhesive with 60%Cu@Ag/40% Ag plates
Fig. 8 Structures of micro-nano copper particles mixed with different particle sizes[90] (a) TEM image showing micron particles; (b) TEM image showing nanoparticles
Fig. 9 Schematic diagram of sintering of bimodal copper slurry under different atmospheres[93]
Fig. 10 Schematic diagram of oxidation effect of surface layer of copper nanoparticles on the sintering performance[94] (a) With CuO outer layer; (b) No CuO outer layer
Fig. 11 Mechanism of promotion in copper slurry by ascorbic acid (AA)[96]
Fig. 12 Schematic diagram of reduction and sintering mechanism of Cu NP paste[98]
Fig. 13 SEM images of cross sections of sintered specimens at different temperatures[102] (a, b) 200 ℃; (c, d) 225 ℃; (e, f) 250 ℃; (g, h) 275 ℃
Fig. 14 Resistivities of the bonding layer at different sintering temperatures[103]
Fig. 15 Schematic diagram of the preparation process of Cu-Cu connection joints[104]
| Particle size | Appearance | Sintering process | Electrical conductivity/ (μΩ·cm) | Shearing performance/ MPa | Ref. |
|---|---|---|---|---|---|
| 10 and 1000 nm particle compound | Irregular | Ar, 250 ℃, 2 MPa, 15 min | 5.44 | 45.6 | [ |
| 200 nm, 1000 nm | Spherical | N2, 350 ℃, 0.4 MPa | - | 40 | [ |
| 530 nm | Irregular | 97% N2-3% H2, 300 ℃, 30 min | - | 23 | [ |
| 60-100 nm | Angular | N2, 200 ℃, 60 min | 18 | - | [ |
| Thick 200 nm, length 3-5 μm | Spherical | N2, 275 ℃, 10 MPa, 30 min | - | 50 | [ |
| 30-400 nm | Angular | N2, 300 ℃, 0.4 MPa, 30 min | - | 24.8 | [ |
| 6.5 nm | Spherical | Ar, 250 ℃, 5 MPa, 30 min | - | 36.2 | [ |
| 100 nm | Spherical | Air, 225 ℃, 8 MPa, 10 min | 59±7 | 28.7±1.6 | [ |
| 500 nm | Angular | HCOOH, 275 ℃, 5 MPa, 30 min | - | 70 | [ |
| 60.5 nm | Spherical | 95% Ar-5% H2, 300 ℃, 1.08 MPa, 60 min | 11.2 | 31.88 | [ |
| 30 nm | Spherical | 95% N2-5% H2, 320 ℃, 10 MPa, 5 min | 3.16 | 51.7 | [ |
| 54-64 nm | Sphere-like | H2, 400 ℃, 1.2 MPa, 5 min | - | 37.7 | [ |
| 5 nm | Sphere-like | 95% Ar-5% H2, 250 ℃, 1.08 MPa, 60 min | 4.1 | 25.36 | [ |
| 400-1200 nm | Sphere-like | Air, 200 ℃, 50 s | 54±2 | - | [ |
| 300-400 nm | Sphere-like | N2, 200 ℃, 30 min | 139±24 | - | [ |
| 1-3 μm | Sphere-like | Air, 180 ℃, 5 min | 30 | - | [ |
| 200 nm | Spherical | Air, 300 ℃, 2 MPa, 1 min | - | 21.8 | [ |
| 50 nm | Spherical | Air, 220 ℃, 5 min | - | 30 | [ |
| 10 nm | Spherical | N2, 200 ℃, 30 min | 14.0±4.5 | - | [ |
| 6.5 nm | Spherical | Air, 175 ℃, 2 MPa, 10 min | - | 35.1 | [ |
| 60 nm | Sphere-like | 95% Ar-5% H2, 250 ℃, 10 MPa, 60 min | - | 32.4 | [ |
| 4.4 nm | Angular | N2, 150 ℃, 30 min | 52 | - | [ |
| Tens to hundreds of nanometers | Irregular | Vacuum, 300 ℃, 0.4 MPa,30 min | - | 20 | [ |
| <10 nm | Angular | Ar, 250 ℃, 3 MPa, 30 min | 5.1 | - | [ |
Table 3 Comparison of various low-temperature sintering processes and their performance
| Particle size | Appearance | Sintering process | Electrical conductivity/ (μΩ·cm) | Shearing performance/ MPa | Ref. |
|---|---|---|---|---|---|
| 10 and 1000 nm particle compound | Irregular | Ar, 250 ℃, 2 MPa, 15 min | 5.44 | 45.6 | [ |
| 200 nm, 1000 nm | Spherical | N2, 350 ℃, 0.4 MPa | - | 40 | [ |
| 530 nm | Irregular | 97% N2-3% H2, 300 ℃, 30 min | - | 23 | [ |
| 60-100 nm | Angular | N2, 200 ℃, 60 min | 18 | - | [ |
| Thick 200 nm, length 3-5 μm | Spherical | N2, 275 ℃, 10 MPa, 30 min | - | 50 | [ |
| 30-400 nm | Angular | N2, 300 ℃, 0.4 MPa, 30 min | - | 24.8 | [ |
| 6.5 nm | Spherical | Ar, 250 ℃, 5 MPa, 30 min | - | 36.2 | [ |
| 100 nm | Spherical | Air, 225 ℃, 8 MPa, 10 min | 59±7 | 28.7±1.6 | [ |
| 500 nm | Angular | HCOOH, 275 ℃, 5 MPa, 30 min | - | 70 | [ |
| 60.5 nm | Spherical | 95% Ar-5% H2, 300 ℃, 1.08 MPa, 60 min | 11.2 | 31.88 | [ |
| 30 nm | Spherical | 95% N2-5% H2, 320 ℃, 10 MPa, 5 min | 3.16 | 51.7 | [ |
| 54-64 nm | Sphere-like | H2, 400 ℃, 1.2 MPa, 5 min | - | 37.7 | [ |
| 5 nm | Sphere-like | 95% Ar-5% H2, 250 ℃, 1.08 MPa, 60 min | 4.1 | 25.36 | [ |
| 400-1200 nm | Sphere-like | Air, 200 ℃, 50 s | 54±2 | - | [ |
| 300-400 nm | Sphere-like | N2, 200 ℃, 30 min | 139±24 | - | [ |
| 1-3 μm | Sphere-like | Air, 180 ℃, 5 min | 30 | - | [ |
| 200 nm | Spherical | Air, 300 ℃, 2 MPa, 1 min | - | 21.8 | [ |
| 50 nm | Spherical | Air, 220 ℃, 5 min | - | 30 | [ |
| 10 nm | Spherical | N2, 200 ℃, 30 min | 14.0±4.5 | - | [ |
| 6.5 nm | Spherical | Air, 175 ℃, 2 MPa, 10 min | - | 35.1 | [ |
| 60 nm | Sphere-like | 95% Ar-5% H2, 250 ℃, 10 MPa, 60 min | - | 32.4 | [ |
| 4.4 nm | Angular | N2, 150 ℃, 30 min | 52 | - | [ |
| Tens to hundreds of nanometers | Irregular | Vacuum, 300 ℃, 0.4 MPa,30 min | - | 20 | [ |
| <10 nm | Angular | Ar, 250 ℃, 3 MPa, 30 min | 5.1 | - | [ |
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