CN103956354A - Interconnecting wire with graphene serving as metallization layer and diffusion barrier layer and manufacturing method of interconnecting wire - Google Patents
Interconnecting wire with graphene serving as metallization layer and diffusion barrier layer and manufacturing method of interconnecting wire Download PDFInfo
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- CN103956354A CN103956354A CN201410194159.1A CN201410194159A CN103956354A CN 103956354 A CN103956354 A CN 103956354A CN 201410194159 A CN201410194159 A CN 201410194159A CN 103956354 A CN103956354 A CN 103956354A
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Abstract
The invention discloses an interconnecting wire with graphene serving as a metallization layer and a diffusion barrier layer. A grapheme layer and a copper-graphene complex phase conducting layer are sequentially arranged on an insulating substrate from top to bottom. A manufacturing method of the interconnecting wire comprises the steps that the grapheme is transferred onto the cleaned insulating substrate, the graphene is patterned with a photoetching method, and the copper-graphene complex phase conducting layer is formed on the graphene in an electroplated mode in electroplating liquid containing graphene nanosheets with an electroplating method. According to the interconnecting wire, the graphene serves as the diffusion barrier layer of the conducting layer, so that the thickness of the diffusion barrier layer is reduced, and miniaturization of a device is facilitated; besides, the surface roughness of the conducting layer can be reduced, the conductivity of the conducting layer is improved, and the interconnecting wire has excellent corrosion resistance. The graphene serves as not only the metallization layer but also the diffusion barrier layer of the conducting layer, so that the manufacturing process is simplified.
Description
Technical field
The present invention relates to a kind of interconnection line, especially a kind ofly take interconnection line that Graphene is metal layer and diffusion barrier layer and preparation method thereof.
Background technology
Existing interconnection line is generally on insulated substrate, to have successively diffusion barrier layer, metal layer and conductive layer from bottom to top.Wherein, diffusion barrier layer is used the nanocrystalline or amorphous barrier layers such as TiNx conventionally, and its object is mainly the diffusion that stops copper.And metal layer is generally chemical plating copper layer, its effect is mainly that the negative electrode of conduction is provided for follow-up copper plating process.The resistance of diffusion barrier layer is conventionally very large, and thermal diffusion performance is also poor, and its thickness is conventionally also larger, and this has reduced the conductivity of interconnection line on the one hand, has increased on the one hand the size of interconnecting construction.The surface roughness of electroplating the interconnection line obtaining on the metal layers such as electroless copper is conventionally larger, can increase the electron scattering of wire, and the resistivity of interconnection line is increased.The double-decker of diffusion barrier layer and metal layer had both increased the complexity of technique, had increased again the size of device, had limited the further miniaturization of device.
Summary of the invention
The object of the present invention is to provide a kind of be conducive to device miniaturization take interconnection line that Graphene is metal layer and diffusion barrier layer and preparation method thereof.
Of the present inventionly take the interconnection line that Graphene is metal layer and diffusion barrier layer and on insulated substrate, have successively graphene layer and copper-graphite alkene complex phase conductive layer from bottom to top.
Above-mentioned insulated substrate is PET or Si/SiO
2substrate.
The preparation method that the Graphene of take is the interconnection line of metal layer and diffusion barrier layer, comprises the following steps:
1) insulated substrate is put into acetone ultrasonic cleaning, and with deionized water rinsing, nitrogen dries up;
2) Graphene is transferred to through step 1) on the insulated substrate processed;
3) use the method for photoetching to step 2) graphene layer graphical, interconnection line figure is transferred on graphene layer;
4) copper electrolyte configuration: copper sulphate water is dissolved, add successively therein sulfuric acid, surfactant and hydrochloric acid, stir, obtain copper electrolyte, concentration of copper sulfate in copper electrolyte is 150-250g/L, sulfuric acid concentration is 40-110 g/L, and chlorine ion concentration is 50-120 ppm, and surfactant concentration is 0.1-2g/L;
5) the copper electrolyte electroplate liquid of graphene-containing configuration: graphene nanometer sheet is first used to a small amount of step 4) wetting and ultrasonic after, join again in remaining copper electrolyte, the concentration of graphene nanometer sheet is 0.01-4g/L, fully stirs, and obtains the electroplate liquid of graphene-containing;
6) electroplate: take phosphorus bronze sheet as anode, step 2) the patterned Graphene of gained is as negative electrode, is placed in step 5) the electroplate liquid of graphene-containing nanometer sheet, adjusting temperature is 10-40
oc, current density are 0.5-16A/dm
2, under stirring condition, electroplate 1-120min, obtaining conductive layer is the interconnection line of copper-graphite alkene complex phase.
Above-mentioned surfactant can be neopelex or lauryl sodium sulfate.Described Graphene can be single or multiple lift
.
The present invention compares the beneficial effect having to be had with background technology:
The present invention compares the beneficial effect having with background technology: the present invention is usingd Graphene as metal layer and diffusion barrier layer, not only reduced the surface roughness of conductive layer, can improve the conductivity of interconnection line, and reduce the thickness of diffusion barrier layer, be conducive to the miniaturization of device.Adopt copper-graphite alkene complex phase as conductive layer, can improve conductivity, antioxygenic property and the decay resistance of interconnection line.Preparation technology of the present invention is simple.
Accompanying drawing explanation
The structural representation of Fig. 1 interconnection line of the present invention.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
As shown in Figure 1, of the present inventionly take the interconnection line that Graphene is metal layer and diffusion barrier layer and on insulated substrate 1, have successively graphene layer 2 and copper-graphite alkene complex phase conductive layer 3 from bottom to top.
Embodiment 1
1) by Si/SiO
2substrate is put into acetone ultrasonic cleaning, is also used deionized water rinsing, and nitrogen dries up stand-by;
2) single-layer graphene is transferred to through step 1) Si/SiO that processes
2on substrate;
3) use the method for photoetching to step 2) graphene layer graphical, interconnection line figure is transferred on graphene layer;
4) copper electrolyte configuration: copper sulphate water is dissolved, add successively therein sulfuric acid, neopelex and hydrochloric acid, stir, obtain plating solution, concentration of copper sulfate in plating solution is 200g/L, sulfuric acid concentration is 40 g/L, and chlorine ion concentration is 100ppm, and neopelex concentration is 0.1g/L;
5) the copper electrolyte electroplate liquid of graphene-containing configuration: graphene nanometer sheet is first used to a small amount of step 4) wetting and ultrasonic after, join again in remaining copper electrolyte, the concentration of graphene nanometer sheet is 0.01g/L, fully stirs, and obtains the electroplate liquid of graphene-containing;
6) electroplate liquid of graphene-containing nanometer sheet plating: take phosphorus bronze sheet as anode, patterned Graphene, as negative electrode, is placed in step 5), regulating temperature is 25
oc, current density are 16A/dm
2, under stirring condition, electroplate 1min, on Graphene surface, obtain copper-graphite alkene complex phase conductive layer.
Embodiment 2
1) base-plate cleaning: pet substrate is put into acetone ultrasonic cleaning, also used deionized water rinsing, and nitrogen dries up stand-by;
2) multi-layer graphene is transferred to through step 1) on the pet substrate processed;
3) use the method for photoetching to step 2) graphene layer graphical, interconnection line figure is transferred on graphene layer;
4) copper electrolyte configuration: copper sulphate water is dissolved, add successively therein sulfuric acid, lauryl sodium sulfate and hydrochloric acid, stir, obtain plating solution, concentration of copper sulfate in plating solution is 150g/L, sulfuric acid concentration is 90 g/L, and chlorine ion concentration is 50 ppm, and lauryl sodium sulfate concentration is 2g/L;
5) the copper electrolyte electroplate liquid of graphene-containing configuration: graphene nanometer sheet is first used to a small amount of step 4) wetting and ultrasonic after, then join in remaining copper electrolyte, the concentration of graphene nanometer sheet is 4g/L, fully stirs, and obtains the electroplate liquid of graphene-containing;
6) electroplate liquid of graphene-containing nanometer sheet plating: take phosphorus bronze sheet as anode, patterned Graphene, as negative electrode, is placed in step 5), regulating temperature is 10
oc, current density are 0.5A/dm
2, under stirring condition, electroplate 120min, on Graphene surface, obtain copper-graphite alkene complex phase conductive layer.
Embodiment 3
1) base-plate cleaning: by Si/SiO
2substrate is put into acetone ultrasonic cleaning, is also used deionized water rinsing, and nitrogen dries up stand-by;
2) single-layer graphene is transferred to through step 1) Si/SiO that processes
2on substrate;
3) use the method for photoetching to step 2) graphene layer graphical, interconnection line figure is transferred on graphene layer;
4) copper electrolyte configuration: copper sulphate water is dissolved, add successively therein sulfuric acid, neopelex and hydrochloric acid, stir, obtain plating solution, concentration of copper sulfate in plating solution is 250g/L, sulfuric acid concentration is 80g/L, and chlorine ion concentration is 120 ppm, and neopelex concentration is 1.5g/L;
5) the copper electrolyte electroplate liquid of graphene-containing configuration: graphene nanometer sheet is first used to a small amount of step 4) wetting and ultrasonic after, then join in remaining copper electrolyte, the concentration of graphene nanometer sheet is 1g/L, fully stirs, and obtains the electroplate liquid of graphene-containing;
6) electroplate liquid of graphene-containing nanometer sheet plating: take phosphorus bronze sheet as anode, patterned Graphene, as negative electrode, is placed in step 5), regulating temperature is 40
oc, current density are 8A/dm
2, under stirring condition, electroplate 20min, on Graphene surface, obtain copper-graphite alkene complex phase conductive layer.
Embodiment 4
1) base-plate cleaning: by Si/SiO
2substrate is put into acetone ultrasonic cleaning, is also used deionized water rinsing, and nitrogen dries up stand-by;
2) single-layer graphene is transferred to through step 1) Si/SiO that processes
2on substrate;
3) use the method for photoetching to step 2) graphene layer graphical, interconnection line figure is transferred on graphene layer;
4) copper electrolyte configuration: copper sulphate water is dissolved, add successively therein sulfuric acid, neopelex and hydrochloric acid, stir, obtain plating solution, concentration of copper sulfate in plating solution is 200g/L, sulfuric acid concentration is 110 g/L, and chlorine ion concentration is 100ppm, and neopelex concentration is 2g/L;
5) the copper electrolyte electroplate liquid of graphene-containing configuration: graphene nanometer sheet is first used to a small amount of step 4) wetting and ultrasonic after, then join in remaining copper electrolyte, the concentration of graphene nanometer sheet is 2g/L, fully stirs, and obtains the electroplate liquid of graphene-containing;
6) electroplate liquid of graphene-containing nanometer sheet plating: take phosphorus bronze sheet as anode, patterned Graphene, as negative electrode, is placed in step 5), regulating temperature is 25
oc, current density are 1A/dm
2, under stirring condition, electroplate 50min, on Graphene surface, obtain copper-graphite alkene complex phase conductive layer.
Embodiment 5
1) base-plate cleaning: by Si/SiO
2substrate is put into acetone ultrasonic cleaning, is also used deionized water rinsing, and nitrogen dries up stand-by;
2) single-layer graphene is transferred to through step 1) Si/SiO that processes
2on substrate;
3) use the method for photoetching to step 2) graphene layer graphical, interconnection line figure is transferred on graphene layer;
4) copper electrolyte configuration: copper sulphate water is dissolved, add successively therein sulfuric acid, neopelex and hydrochloric acid, stir, obtain plating solution, concentration of copper sulfate in plating solution is 200g/L, sulfuric acid concentration is 65 g/L, and chlorine ion concentration is 100ppm, and neopelex concentration is 1.2g/L;
5) the copper electrolyte electroplate liquid of graphene-containing configuration: graphene nanometer sheet is first used to a small amount of step 4) wetting and ultrasonic after, then join in remaining copper electrolyte, the concentration of graphene nanometer sheet is 3g/L, fully stirs, and obtains the electroplate liquid of graphene-containing;
6) electroplate liquid of graphene-containing nanometer sheet plating: take phosphorus bronze sheet as anode, patterned Graphene, as negative electrode, is placed in step 5), regulating temperature is 25
oc, current density are 2A/dm
2, under stirring condition, electroplate 60min, on Graphene surface, obtain copper-graphite alkene complex phase conductive layer.
Claims (5)
1. the interconnection line that the Graphene of take is metal layer and diffusion barrier layer, is characterized in that on insulated substrate (1), having successively graphene layer (2) and copper-graphite alkene complex phase conductive layer (3) from bottom to top.
2. according to claim 1ly take the interconnection line that Graphene is metal layer and diffusion barrier layer, it is characterized in that: described insulated substrate (1) is PET or Si/SiO
2substrate.
3. prepare the method that Graphene is the interconnection line of metal layer and diffusion barrier layer of take as claimed in claim 1, it is characterized in that comprising the following steps:
1) insulated substrate is put into acetone ultrasonic cleaning, and with deionized water rinsing, nitrogen dries up;
2) Graphene is transferred to through step 1) on the insulated substrate processed;
3) use the method for photoetching to step 2) graphene layer graphical, interconnection line figure is transferred on graphene layer;
4) copper electrolyte configuration: copper sulphate water is dissolved, add successively therein sulfuric acid, surfactant and hydrochloric acid, stir, obtain copper electrolyte, concentration of copper sulfate in copper electrolyte is 150-250g/L, sulfuric acid concentration is 40-110 g/L, and chlorine ion concentration is 50-120 ppm, and surfactant concentration is 0.1-2g/L;
5) the copper electrolyte electroplate liquid of graphene-containing configuration: graphene nanometer sheet is first used to a small amount of step 4) wetting and ultrasonic after, join again in remaining copper electrolyte, the concentration of graphene nanometer sheet is 0.01-4g/L, fully stirs, and obtains the electroplate liquid of graphene-containing;
6) electroplate: take phosphorus bronze sheet as anode, step 2) the patterned Graphene of gained is as negative electrode, is placed in step 5) the electroplate liquid of graphene-containing nanometer sheet, adjusting temperature is 10-40
oc, current density are 0.5-16A/dm
2, under stirring condition, electroplate 1-120min, obtaining conductive layer is the interconnection line of copper-graphite alkene complex phase.
4. according to claim 3ly take the preparation method that Graphene is the interconnection line of metal layer and diffusion barrier layer, it is characterized in that: described surfactant is neopelex or lauryl sodium sulfate.
5. according to claim 3ly take the preparation method that Graphene is the interconnection line of metal layer and diffusion barrier layer, it is characterized in that: described Graphene is single or multiple lift.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911652A (en) * | 2015-04-16 | 2015-09-16 | 西南石油大学 | Nickel, tungsten and graphene composite plating solution, plated film and making method of plated film |
| WO2019119958A1 (en) * | 2017-12-21 | 2019-06-27 | 秦皇岛京河科学技术研究院有限公司 | Preparation method for sic power diode device and structure of sic power diode device |
| US10750619B2 (en) | 2017-12-21 | 2020-08-18 | Industrial Technology Research Institute | Metallization structure and manufacturing method thereof |
| US11908734B2 (en) | 2021-10-06 | 2024-02-20 | International Business Machines Corporation | Composite interconnect formation using graphene |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593097A (en) * | 2012-02-27 | 2012-07-18 | 北京大学 | Integrated circuit metal interconnecting structure and manufacture method thereof |
| CN103265018A (en) * | 2013-05-21 | 2013-08-28 | 上海大学 | Method for directly preparing graphene on insulation base |
| KR20140003218A (en) * | 2012-06-29 | 2014-01-09 | 세종대학교산학협력단 | Method for forming stacked graphene, stacked graphene thereof, and devices including the same |
-
2014
- 2014-05-09 CN CN201410194159.1A patent/CN103956354A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102593097A (en) * | 2012-02-27 | 2012-07-18 | 北京大学 | Integrated circuit metal interconnecting structure and manufacture method thereof |
| KR20140003218A (en) * | 2012-06-29 | 2014-01-09 | 세종대학교산학협력단 | Method for forming stacked graphene, stacked graphene thereof, and devices including the same |
| CN103265018A (en) * | 2013-05-21 | 2013-08-28 | 上海大学 | Method for directly preparing graphene on insulation base |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911652A (en) * | 2015-04-16 | 2015-09-16 | 西南石油大学 | Nickel, tungsten and graphene composite plating solution, plated film and making method of plated film |
| WO2019119958A1 (en) * | 2017-12-21 | 2019-06-27 | 秦皇岛京河科学技术研究院有限公司 | Preparation method for sic power diode device and structure of sic power diode device |
| US10750619B2 (en) | 2017-12-21 | 2020-08-18 | Industrial Technology Research Institute | Metallization structure and manufacturing method thereof |
| US11908734B2 (en) | 2021-10-06 | 2024-02-20 | International Business Machines Corporation | Composite interconnect formation using graphene |
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Application publication date: 20140730 |