CN111785682B - Method for 3D printing of all-carbon three-dimensional multilayer integrated circuit - Google Patents

Method for 3D printing of all-carbon three-dimensional multilayer integrated circuit Download PDF

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CN111785682B
CN111785682B CN202010652758.9A CN202010652758A CN111785682B CN 111785682 B CN111785682 B CN 111785682B CN 202010652758 A CN202010652758 A CN 202010652758A CN 111785682 B CN111785682 B CN 111785682B
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printing
integrated circuit
carbon
dimensional multilayer
multilayer integrated
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CN111785682A (en
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韩拯
董宝娟
陈茂林
李小茜
张桐耀
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Shanxi University
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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K19/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00
    • H10K19/201—Integrated devices having a three-dimensional layout, e.g. 3D ICs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/76867—Barrier, adhesion or liner layers characterized by methods of formation other than PVD, CVD or deposition from a liquids
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K19/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00
    • H10K19/10—Integrated devices, or assemblies of multiple devices, comprising at least one organic element specially adapted for rectifying, amplifying, oscillating or switching, covered by group H10K10/00 comprising field-effect transistors

Abstract

The invention belongs to the field of application research of microelectronics, chips, integrated circuits and the like, and particularly relates to a method for 3D printing of an all-carbon three-dimensional multilayer integrated circuit. The method is based on a 3D printing technology, realizes direct printing and in-situ electrode interconnection of a three-dimensional multilayer integrated circuit in a multi-layer and cross-scale manner in a spray printing mode, and specifically comprises the following steps: decomposing a vector integrated circuit which is designed in advance into a plurality of layers within a printing precision range, mixing semiconductor carbon-based nano materials, metallic carbon-based nano materials, insulating carbon-based nano materials and solvent polymers which are alternately used as raw materials from a first layer, automatically selecting raw materials with corresponding electrical characteristics according to the materials required by the integrated circuit in the layers, and printing and curing the required integrated circuit in situ by using a corresponding high-precision nozzle and combining a high-precision positioning platform; and finally, forming the target three-dimensional multilayer integrated circuit until each image layer is accurately positioned, printed and solidified.

Description

Method for 3D printing of all-carbon three-dimensional multilayer integrated circuit
Technical Field
The invention belongs to the field of application research of microelectronics, chips, integrated circuits and the like, and particularly relates to a method for 3D printing of an all-carbon three-dimensional multilayer integrated circuit.
Background
Since the first demonstration of the metal oxide semiconductor field effect transistor in 1960, the technology of etching, processing and the like from top to bottom of a silicon-based semiconductor with a Complementary Metal Oxide Semiconductor (CMOS) circuit as a core forms an important basis of the modern computer technology, namely the skyscraper. At present, the mainstream silicon semiconductor technology adopts a 3D integration mode no matter a logic chip or a memory chip, namely, a multilayer circuit is adopted, and the integration density of field effect transistors on the chip is greatly improved in an interlayer interconnection mode.
With the rapid development of modern microelectronic technology, the market demands for innovative technologies such as new-concept devices and new-concept manufacturing methods are increasingly prominent. Especially, under the large background that the nano-processing technology approaches the precision limit and the moore's law is more and more difficult, the development trend of the semiconductor industry in the later moore times will focus on the exploration in the directions of atomic manufacturing, additive manufacturing, multifunctional nano-compounding and the like. As is well known, the conventional semiconductor processing technology adopts the core process route of "top-down" and "material reduction manufacturing", in which multiple necessary steps of silicon wafer and other substrates, photoresist, mask, electrode evaporation and stripping in solution are adopted. The complicated processing steps have severe requirements on the cleanliness of the processing environment, and complex matched processing and the like are required among corresponding devices.
At present, the number of patents related to the additive manufacturing of semiconductor integrated circuits in China is very small. There are patents in the united states of america that are the primary country of invention for 3D printing techniques involving some semiconductor circuits. For example, aerosol jet printing technology developed by Optomec corporation of america (US patent US20140342082 A1) can effectively produce 3D printed electronic products. By adopting the AJ300 series Aerosol jet3D printer of the company, research teams of Duke university and Manchester university in the United kingdom successfully print out the composite thin film transistor based on materials such as silver nanowires, boron nitride nanosheets and carbon nanotubes with 200-micrometer wide conductive channels in 2019, and corresponding results are published in ACSNano academic journal (DOI: 10.1021/acsano.9b04337). To date, no 3D printing technology for integrated devices based on all-carbon materials, especially all-carbon three-dimensional integrated circuits, has been reported.
Aiming at the background, the invention provides a 3D printing manufacturing method of an all-carbon three-dimensional multilayer integrated circuit, which adopts a process route taking 'bottom-up' and 'additive manufacturing' as cores, and a direct-writing 3D printing process which does not need photoresist, mask plate, electrode evaporation, stripping and other steps is omitted. The invention has low cost and simple device, can print integrated semiconductor circuits in multiple layers and can achieve the aim of vertical 3D integrated large-scale circuits. The technology of the invention can be further expanded to any substrate (flexible substrate, functional material substrate, etc.), and large-scale integrated circuits can be prepared under lower environmental requirements.
Disclosure of Invention
The invention aims to provide a method for 3D printing (micro-nano scale additive manufacturing) of an all-carbon three-dimensional multilayer integrated circuit, and the universality of the method is proved by successfully preparing various channel semiconductor material systems. The method can realize stable and controllable printing of the three-dimensional multilayer integrated circuit on a large-area, multilayer and arbitrary substrate. The size of the integrated circuit framework can be any size from micro-nano scale to macro-millimeter scale and the like. The structure is completely consistent with that of the traditional silicon-based three-dimensional multilayer integrated circuit, but the structure is not limited by a hard substrate, and the printing can be carried out on any base such as a flexible substrate, a transparent substrate and the like. The printed all-carbon integrated circuit has logic operation capability directly, can realize the integration of semiconductor devices and various photoelectric components, and each functional component adopts a 3D printing method, and realizes the printing and interconnection of various carbon-based media by changing printing raw materials or needles and other methods.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for 3D printing of an all-carbon three-dimensional multilayer integrated circuit is based on a 3D printing (additive manufacturing) technology, adopts a spray printing mode, is multi-level and cross-scale, and realizes direct printing and in-situ electrode interconnection of the three-dimensional multilayer integrated circuit, and comprises the following specific steps:
step 1, vector graphic output: decomposing a vector integrated circuit which is designed in advance into a plurality of layers within a printing precision range, mixing a semiconductor carbon-based nano material, a metallic carbon-based nano material, an insulating carbon-based nano material and a solvent polymer which are alternately used as raw materials from the first layer, automatically selecting raw materials with corresponding electrical characteristics according to the materials required by the integrated circuit in the layers, and printing and curing the required integrated circuit in situ by using a corresponding high-precision nozzle and combining a high-precision positioning platform;
and 2, repeating the step 1 until each image layer is accurately positioned, printed and solidified, and finally forming the target three-dimensional multilayer integrated circuit.
Further, the spray printing may be replaced with photo-curing liquid-phase printing, or a mixture of inkjet printing and photo-curing liquid-phase printing may be used.
Further, the semiconductor carbon-based nanomaterial in step 1 is one of a p-type single-walled carbon nanotube material or an n-type single-walled carbon nanotube material. The single-walled carbon nanotube can be prepared by an arc discharge method or a chemical vapor deposition method. The arc discharge method is to mix metal powder in graphite, the arc discharge time is between 1 and 30min, and the power output is between 750 and 3000W, so as to prepare the single-walled carbon nanotube; the chemical vapor deposition method comprises introducing methane (CH) into 140cm quartz tube 4 ) At 800 ℃, methane is cracked and nucleated under the action of iron simple substance (Fe) to grow the carbon nano tube. Single-walled carbon nanotubes exhibit metallic or semiconducting properties based on their chirality, and thus a separation process is generally required to obtain high-purity semiconducting carbon nanotubes. The separation process generally comprises dispersing 5mg of carbon nanotubes in 3000mL of aqueous solution containing 1% of sodium dodecyl sulfate or sodium dodecyl benzene sulfonate and other surfactants, and then performing ultrasonic treatment, centrifugation and other processes, such as density gradient ultracentrifugation, gel chromatography separation or non-covalent polymer modification separation, to realize the separation of carbon nanotubes with different diameters, conductive properties and even chiral indexes. Doping of carbon nanotubes with boron or nitrogen can result in p-type or n-type behavior, respectively, n-type carbon nanotubes can also be prepared by pyrolysis of melamine by chemical vapor deposition at elevated temperatures of 300-980 ℃ under argon.
Further, in the step 1, the metallic carbon-based nanomaterial is graphene nanopowder or metallic carbon nanotubes. Based on the preparation and separation method of the carbon nano-tube in the previous step, the carbon nano-tube with excellent metallicity is obtained.
Further, the insulating carbon-based nanomaterial in step 1 is graphene oxide or an insulating carbon nanotube.
Further, the solvent polymer in step 1 may be a thermosetting liquid resin or an active substance photosensitive glue.
Further, the curing in the step 1 is divided into heating curing for thermosetting liquid resin and ultraviolet illumination curing for active substance photosensitive adhesive; the temperature for heating and curing the thermosetting liquid resin is 20-300 ℃.
Furthermore, the sequence and the interconnection mode between layers of the target three-dimensional multilayer integrated circuit in the step 2 are not limited. For example, may comprise any number of layers of MOSFETs, any number of layers of functional or heat dissipating units, etc. The characteristic is different from 3D integration of a silicon-based semiconductor chip, and only one layer of the bottom layer of the silicon-based semiconductor chip is provided with an MOSFET (metal oxide semiconductor field effect transistor) at present.
Compared with the prior art, the invention has the following advantages:
1) The method prints the full-carbon large-scale integrated circuit by a bottom-up additive manufacturing method, can avoid the dependence of the traditional processing process on complex and severe manufacturing environment, has low manufacturing cost of printing equipment and wide application material range.
2) The raw materials are all from carbon-based nano materials (graphene, graphene oxide, carbon nano tubes and the like), the material is suitable for various substrates except a silicon substrate, and the material is green and environment-friendly and is compatible with application scenes of flexible chips and the like.
Drawings
FIG. 1 is a process scheme of the present invention;
FIG. 2 is a schematic view of the apparatus of the present invention; the logic unit comprises 1,2, a Semiconductor carbon-based nano material, a metallic carbon-based nano material and an insulating carbon-based nano material, 3, 4, 5, 6, 7 and S letters, wherein the feeding "ink" is mixed with 1 and 2, the high-precision nozzle is arranged, the high-precision positioning platform is arranged, the multilayer three-dimensional interconnection integrated circuit is arranged, the basic MOSFET logic unit schematic diagram in the circuit is arranged, and the M, I and S letters respectively represent a Metal, an Insulator and a Semiconductor.
Detailed Description
Example 1
A3D printing method of an all-carbon three-dimensional multilayer integrated circuit is based on a 3D printing technology, and adopts a spray printing mode to realize direct printing and in-situ electrode interconnection of the three-dimensional multilayer integrated circuit in a multi-layer and cross-scale mode, and comprises the following specific steps:
step 1, outputting a vector graph: decomposing a vector integrated circuit which is designed in advance into a plurality of layers within a printing precision range, mixing a p-type single-walled carbon nanotube material, graphene nano powder, graphene oxide and thermosetting liquid resin alternately from a first layer to prepare ink as a raw material, automatically selecting a raw material with corresponding electrical characteristics according to the material required by the integrated circuit in the layer, and printing in situ by using a corresponding high-precision nozzle and combining a high-precision positioning platform to obtain the required integrated circuit;
and 2, repeating the step 1 until each image layer is accurately positioned, printed and thermally cured in a thermal curing mode, and heating and curing at 20 ℃ to finally form the target three-dimensional multilayer integrated circuit.
Example 2
A method for 3D printing of an all-carbon three-dimensional multilayer integrated circuit is based on a 3D printing technology, and direct printing and in-situ electrode interconnection of the three-dimensional multilayer integrated circuit are achieved in a multi-layer and cross-scale mode in a photocuring liquid phase printing mode, and a substrate can be a flexible substrate. The method comprises the following specific steps:
step 1, outputting a vector graph: decomposing a vector integrated circuit which is designed in advance into a plurality of layers within a printing precision range,
from a first image layer, preparing 'ink' by alternately using an n-type single-walled carbon nanotube material, graphene nano powder, graphene oxide and active substance photosensitive adhesive to mix as raw materials, automatically selecting the raw materials with corresponding electrical characteristics according to the materials required by the integrated circuit in the image layer, using a corresponding high-precision extrusion type needle head, combining a high-precision positioning platform, printing the raw materials on a flexible substrate in situ, and curing the raw materials by ultraviolet light to obtain the required flexible integrated circuit;
and 2, repeating the step 1 until each image layer is accurately positioned, printed and solidified, and finally forming the target flexible three-dimensional multilayer integrated circuit.
Example 3
A3D printing method of an all-carbon three-dimensional multilayer integrated circuit is based on a 3D printing technology, and adopts a spray printing mode to realize direct printing and in-situ electrode interconnection of the three-dimensional multilayer integrated circuit in a multi-layer and cross-scale mode, and comprises the following specific steps:
step 1, outputting a vector graph: decomposing a vector integrated circuit which is designed in advance into a plurality of layers within a printing precision range, mixing a p-type single-walled carbon nanotube material, graphene nano powder, graphene oxide and thermosetting liquid resin alternately from a first layer to prepare ink as a raw material, automatically selecting a raw material with corresponding electrical characteristics according to the material required by the integrated circuit in the layer, and printing in situ by using a corresponding high-precision nozzle and combining a high-precision positioning platform to obtain the required integrated circuit;
and 2, repeating the step 1 until each image layer is accurately positioned, printed and thermally cured in a thermal curing mode, and heating and curing at 100 ℃ to finally form the target three-dimensional multilayer integrated circuit.
Example 4
A3D printing method of an all-carbon three-dimensional multilayer integrated circuit is based on a 3D printing technology, and adopts a spray printing mode to realize direct printing and in-situ electrode interconnection of the three-dimensional multilayer integrated circuit in a multi-layer and cross-scale mode, and comprises the following specific steps:
step 1, outputting a vector graph: decomposing a vector integrated circuit which is designed in advance into a plurality of layers within a printing precision range, mixing a p-type single-walled carbon nanotube material, graphene nano powder, graphene oxide and thermosetting liquid resin alternately from a first layer to prepare ink as a raw material, automatically selecting a raw material with corresponding electrical characteristics according to the material required by the integrated circuit in the layer, and printing in situ by using a corresponding high-precision nozzle and combining a high-precision positioning platform to obtain the required integrated circuit;
and 2, repeating the step 1 until each layer is accurately positioned, printed and thermally cured at 300 ℃ to finally form the target three-dimensional multilayer integrated circuit.

Claims (8)

1. A3D printing method of an all-carbon three-dimensional multilayer integrated circuit is characterized in that based on a 3D printing technology, direct printing and in-situ electrode interconnection of the three-dimensional multilayer integrated circuit are realized in a multi-layer and cross-scale mode in a spray printing mode, and the method comprises the following specific steps:
step 1, outputting a vector graph: decomposing a vector integrated circuit which is designed in advance into a plurality of layers within a printing precision range, from a first layer, mixing a semiconductor carbon-based nano material, a metallic carbon-based nano material, an insulating carbon-based nano material and a solvent polymer alternately to prepare ink as raw materials, automatically selecting the raw materials with corresponding electrical characteristics according to the materials required by the integrated circuit in the layers, and printing and curing the required integrated circuit in situ by using a corresponding extrusion type needle head or a high-precision nozzle and combining a high-precision positioning platform;
and 2, repeating the step 1 until each image layer is accurately positioned, printed and solidified, and finally forming the target three-dimensional multilayer integrated circuit.
2. The method for 3D printing of the all-carbon three-dimensional multilayer integrated circuit according to claim 1, wherein the spray printing is replaced by photo-curing liquid-phase printing or a mixture of ink-jet printing and photo-curing liquid-phase printing is used.
3. The method of claim 1, wherein the semiconductor carbon-based nanomaterial of step 1 is one of a p-type single-walled carbon nanotube material or an n-type single-walled carbon nanotube material.
4. The method for 3D printing of the all-carbon three-dimensional multilayer integrated circuit according to claim 1, wherein the metallic carbon-based nanomaterial in step 1 is graphene nanopowder or metallic carbon nanotubes.
5. The method for 3D printing of the all-carbon three-dimensional multilayer integrated circuit according to claim 1, wherein the insulating carbon-based nanomaterial in the step 1 is graphene oxide or insulating carbon nanotubes.
6. The method for 3D printing the all-carbon three-dimensional multilayer integrated circuit according to claim 1, wherein the solvent polymer in the step 1 is a thermosetting liquid resin or an active substance photosensitive glue.
7. The method for 3D printing the all-carbon three-dimensional multilayer integrated circuit according to claim 1, wherein the curing in the step 1 is divided into heating curing for thermosetting liquid resin, and ultraviolet irradiation curing for active substance photosensitive glue; the temperature for heating and curing the thermosetting liquid resin is 20-300 ℃.
8. The method for 3D printing the all-carbon three-dimensional multilayer integrated circuit according to claim 1, wherein the sequence and interconnection manner among the layers of the target three-dimensional multilayer integrated circuit in the step 2 are not limited.
CN202010652758.9A 2020-07-08 2020-07-08 Method for 3D printing of all-carbon three-dimensional multilayer integrated circuit Active CN111785682B (en)

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