CN116969425A - Two-dimensional amorphous carbon nitride material, preparation method thereof, film and electronic device - Google Patents

Two-dimensional amorphous carbon nitride material, preparation method thereof, film and electronic device Download PDF

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CN116969425A
CN116969425A CN202310777120.1A CN202310777120A CN116969425A CN 116969425 A CN116969425 A CN 116969425A CN 202310777120 A CN202310777120 A CN 202310777120A CN 116969425 A CN116969425 A CN 116969425A
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carbon nitride
nitride material
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杨树斌
王海洋
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Beihang University
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Abstract

The invention discloses a two-dimensional amorphous carbon nitride material, a preparation method thereof, a film and an electronic device, wherein the carbon nitride material has a two-dimensional morphology and an amorphous structure. The preparation method of the carbon nitride material comprises the following steps: etching the A component in the MAX phase material by adopting an etchant to obtain an MXene material; and mixing the MXene material with metal bromide and/or bromine gas, and sintering at a preset temperature to obtain the carbon nitride material. The invention provides a novel carbon nitride material with different structures, which shows ultralow dielectric constant and has application value in electronic devices and electronic devices, in particular to flexible electronic devices or communication devices.

Description

Two-dimensional amorphous carbon nitride material, preparation method thereof, film and electronic device
Technical Field
The invention belongs to the field of new materials, and particularly relates to a two-dimensional amorphous carbon nitride material, a preparation method thereof, a film and an electronic device.
Background
With the rapid development of integrated circuits, the size of electronic devices is continually shrinking to the nanometer scale. However, the parasitic capacitance induced by the interconnection increases significantly, decreasing the response speed of the circuit and increasingPower consumption. According to the equationThe parasitic capacitance (C) is proportional to the dielectric constant (k) of the dielectric material between the metal layers (a and d are the sample contact area and the distance between the two metal layers of the capacitor, respectively). Common dielectric material silicon dioxide (SiO 2 ) Is an integrated circuit dielectric material (κ) recommended by the international device and system roadmap (IRDS) and has a dielectric constant of about 4<2) Twice as many as (by 2028), hampering its use in next generation integrated circuits.
To reduce the dielectric constant, dielectric material development has taken some effective strategies such as reducing the polarization by introducing heteroatoms, reducing the density by introducing porosity, and reducing the crystallinity by increasing the amorphous phase. In particular, the introduction of porosity and amorphous phase will greatly alter the local environment, providing low dielectric materials with k values of 2.2-3.5. In the case of introducing porosity, the dielectric material can be considered as a material having two components, wherein the solid backbone component has a dielectric constant close to that of the compact prototype, while the second component (pore) has a dielectric constant of 1. In the case of the introduction of an amorphous phase, the local coordination environment will be rich, which enables to reduce the electron polarization in the dielectric material and thus significantly reduce their dielectric constant. For example, have a high sp 3 Amorphous carbon material with C level (35%) has low kappa number (3) because of sp 3 Localized electrons of atomic orbitals limit electron polarization. However, at sp 3 At a C-C level > 50%, the amorphous carbon density is from 1.7 to 2.3g cm -3 Increasing to 3.0-3.5 g cm -3 Resulting in an increase in kappa number to 6.5. Development of a composition having < 1.0g cm -3 Is desirably low in density and has high sp 3 The amorphous structure low-carbon-based dielectric material with the content of C is an important research and development direction.
Disclosure of Invention
The invention aims at providing a carbon nitride material with ultralow dielectric constant, which has a two-dimensional morphology and an amorphous structure.
In some embodiments, the carbon nitride material has a thickness of 5nm or less.
In some embodiments, XPS testing of the carbon nitride material shows that it includes sp 3 Hybrid C-N bond and sp 2 And (3) hybridization of C-N bonds.
In some embodiments, the spherical electron microscope diffraction image of the carbon nitride material is free of diffraction spots.
In some embodiments, the spherical aberration electron microscope image of the carbon nitride material shows no lattice fringes.
In some embodiments, the XRD pattern of the carbon nitride material has dispersed diffraction peaks between 20 and 30.
In some embodiments, the carbon nitride material has a dielectric constant of 2 or less, preferably 1.7 or less.
In some embodiments, the carbon nitride material has a density of 1g/cm or less 3 Preferably 0.6g/cm or less 3 。
The second aspect of the present invention provides a method for preparing the above carbon nitride material, which is characterized by comprising the steps of: etching the A component in the MAX phase material by adopting a first etchant to obtain an MXene material; mixing the MXene material with a second etchant metal bromide and/or bromine gas, and sintering at a preset temperature to obtain a carbon nitride material; the MAX phase material consists of M, A and X elements, M is one or more of transition metal elements, A is selected from metal elements of a third main group or a fourth main group, and X is carbon and nitrogen.
In some embodiments, the etchant is HF, HCl, HBr, HI, I 2 One or more of fluoride salt + hydrochloric acid, metal halide salt; preferably, the first etchant is HF or HCl;
in some embodiments, the second etchant etches at a temperature between 280 ℃ and 1000 ℃ and/or for an etch time of ≡60min.
The third aspect of the present invention provides a film comprising the above carbon nitride material; or, the carbon nitride material obtained by the preparation method; or consists of the carbon nitride material or the carbon nitride material obtained by the preparation method.
In some embodiments, the dielectric constant of the film is 2 or less; preferably 1.7 or less.
In some embodiments, the film has a breakdown strength of 5MV cm or more -1 。
In some embodiments, the film is an insulating material.
In some embodiments, the thickness of the film is greater than or equal to 3nm; preferably, the thickness is between 3nm and 100 μm; and still more preferably between 3nm and 25 μm.
A fourth aspect of the present invention provides an electronic device comprising the carbon nitride material described above; or the carbon nitride material obtained by the preparation method; or, the film described above.
In some embodiments, the electronic device has flexibility.
In a fifth aspect, the present invention provides an integrated circuit comprising the above carbon nitride material, or the above thin film, or the above electronic device.
In a sixth aspect, the present invention provides a communication device comprising the above carbon nitride material, or the above film, or the above electronic component. The communication device can be a wireless communication device such as a mobile phone, a computer, a base station, etc.
The invention etches the MXene material containing carbon and nitrogen by metal bromide and/or bromine gas to obtain a two-dimensional amorphous carbon nitride material (a-CN) which has low density (0.55 g cm) -3 ) Is far lower than the density (1.0-2.3 gcm) of other amorphous materials -3 ) The higher sp 3C content (-35.7%) results in a significant reduction of electron polarization. This unique structure allows a-CN to exhibit an ultra-low dielectric constant, a value of 1.69 at 100kHz, lower than reported dielectric materials (-4). That is, the present invention provides a novel carbon nitride material having a different structure, which exhibits an ultra-low dielectric constant, and has application value in electronic devices, integrated circuits, and particularly in flexible electronic devices or devices.
Drawings
FIG. 1 shows the composition of the present invention (a) of Ti 3 AlCN to MXene-Ti 3 CNT x Process for converting topology into amorphous a-CNIntent; (b) Ti (Ti) 3 AlCN、MXene-Ti 3 CNT x And an XRD pattern of a-CN powder; (c) Bromine vapor etching of MXene-Ti 3 CNT x Raman spectra at different times.
FIG. 2 shows (a) MXene-Ti obtained in the examples of the present invention 3 CNT x And (b) a photograph of a-CN.
FIG. 3 is a schematic diagram of an embodiment of the present invention made of MXene-Ti 3 CNT x XRD spectra of the product at different etching times during the topological transformation to a-CN.
FIG. 4 is a representation of a-CN in an embodiment of the invention, wherein (a) a TEM image of a-CN nanoplatelet; (b) A Selected Area Electron Diffraction (SAED) image over an area of 200nm diameter, showing a diffuse pattern without diffraction points and polycrystalline rings; (c) a spherical aberration corrected high resolution bright field TEM image; (d) Displaying a disordered atomic arrangement for the magnified image of the red frame marker region in (c); (e) For the fast fourier transform of the selected region of (c), a typical diffusion diffraction pattern of the amorphous layer is shown.
FIG. 5 is a schematic illustration of MXene-Ti in an embodiment of the invention 3 CNT x (a) a TEM image and (b) a SAED image.
Fig. 6 is an (a) STEM image of an a-CN layer and an EDS image of (b) carbon element and (c) nitrogen element in a red region of (a) in an embodiment of the present invention, showing uniform distribution of carbon and nitrogen elements.
FIG. 7 is a representation of the coordination structure, a-CN and g-C, in an embodiment of the invention 3 N 4 (a) carbon and (b) nitrogen K-edge XANES spectra; a-CN and g-C 3 N 4 (C) a C1s high resolution XPS spectrum, (d) a raman spectrum, and (e) a FTIR spectrum; (f) a-CN and g-C 3 N 4 The film resistance curve of (2) shows high resistance.
FIG. 8 is an N1s high resolution spectrum of a-CN in an example of the invention, showing the presence of pyridine N (398.6 eV), pyrrole N (400.0 eV) and graphite N (401.6 eV).
FIG. 9 shows (a) a-CN and g-C in the embodiment of the invention 3 N 4 The XPS spectrum of (2) shows that C, N and O elements are reserved in the a-CN atomic layer; (b) MXene-Ti 3 CNT x Is indicative of the presence of Ti, C, N, O, F and Cl elements.
FIG. 10 shows (a) a-CN and (b) a-C-Ti obtained by vacuum filtration in the examples of the present invention 3 C 2 T x Cross-sectional SEM images of the films show the horizontal orientation of the films produced.
FIG. 11 is a representation of an a-CN atomic layer as a low- κ dielectric material in an embodiment of the invention; (a) Typical current-voltage curves for a-CN atomic layer (4.2 nm), AFM set to Peak force Tunnel mode (PF-TUNA), inset to test setup schematic; (b) The breakdown strength statistical distribution (inset) based on the breakdown voltage data shows the regions with 75% and 100% distribution relative to the average, the top and bottom lines representing the maximum and minimum values; (c) a-CN, tauc plot (inset) of the UV visible near infrared diffuse reflectance spectrum. (d) Capacitance-voltage curves of metal-insulator (310 nm thick a-CN film) -metal structure at different frequencies; (e) a-CN film with a thickness of 310nm, and the dielectric constant of the film is a function of frequency; (f) The dielectric constants of a-CN (red histogram) and the reported low- κ materials in this work are compared.
FIG. 12 is a graph of AFM images of (a) a-CN and (b) corresponding peak currents in an embodiment of the invention; (c) a-CN height distributions (# 1 and # 2); (d) I-V curves collected on AFM image #2 of (a).
FIG. 13 shows (a) a current-voltage curve and (b) a corresponding current-field strength curve for an a-CN film having a thickness of about 310nm in an embodiment of the invention.
Detailed Description
The technical scheme of the invention is described below through specific examples. It is to be understood that the reference to one or more steps of the invention does not exclude the presence of other methods and steps before or after the combination of steps, or that other methods and steps may be interposed between the explicitly mentioned steps. It should also be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Unless otherwise indicated, the numbering of the method steps is for the purpose of identifying the method steps only and is not intended to limit the order of arrangement of the method steps or to limit the scope of the invention, which relative changes or modifications may be regarded as the scope of the invention which may be practiced without substantial technical content modification.
The raw materials and instruments used in the examples are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
Raw materials: mo (99.5%, 10 μm, ara Ding Shiji), ti (99.99%, 300 mesh, ara Ding Ji), al (99.95%, 25 μm, aladin reagent), graphite (99.9%, 10 mesh, alfa Aesar), HCl (35% 37%, beijing reagent), H 2 SO 4 (98%, beijing reagent, HF (48% 51%, innochem reagent), naF (99.9%, aladin reagent), znCl 2 (anhydrous, 98%, innochem reagent), isopropanol (99.5%, innochem reagent), nylon membrane filters (50 mm,0.22 μm, shanghai New sub-purification plant Co., ltd.), anodic Aluminum Oxide (AAO) templates (200 nm pore size, whatman), silicon wafers (boron dopant, < 0.005. OMEGA. Cm, 500.+ -. 25 μm thickness, cis-generated). MAX phase Ti 3 AlC 2 、Ti 3 AlCN and Mo 2 Ga 2 C was purchased from Beijing Sanchuan Enable technology Co.
MAX phase Mo 2 Ti 2 AlC 3 Is synthesized by the following steps: according to the reported method, mo, ti, al and graphite powders were mixed in a ratio of 2:2:1.3:2.7 and sealed in an agate container in a glove box, and milled at 600rpm for 20h. The mixed powder was heated to 1600 ℃ at a rate of 5 ℃/min and maintained under Ar gas flow for 4 hours. After cooling, the sintered body was ground and sieved with 200 mesh.
Carbon nitride of comparative sample (g-C) 3 N 4 ) Is synthesized by the following steps: synthesis of bulk g-C by pyrolysis of urea at 500℃for 2 hours 3 N 4 . Yellow g-C obtained by sonication in isopropanol 3 N 4 。
XRD patterns were performed on a Rigaku D/MAX-2500 diffractometer (Cu K.alpha. Radiation). SEM images were obtained using a zeiss Gemini SEM 500 field emission scanning electron microscope. TEM and STEM-EDS elemental mapping images were collected in a FEI-Tecnai F30 microscope operating at 300kV and at 200X 200nm 2 Obtain an electron diffraction image of the selected region on the region of (a). Aberration corrected high resolution bright field TEM image with alpha monochromator and fifth order aberration correctorCollected in a monochrome Nion HERMES-100 microscope. Raman spectra were measured on a LabRAM HR Evolution raman spectrometer using 633nm excitation laser. Elemental analysis measurements were performed on a Vario EL cube. C and N K edge XANES spectra were obtained at the MCD end station of the BL12B-a beam line located in National Synchrotron Radiation Laboratory (NSRL) of chinese joint fertilizer. EPR spectra were measured by Bruker A300-10/12 instrument. XPS spectra were obtained on a Thermo Scientific Escalab250Xi spectrometer. FTIR spectra were collected on a ThermoFisher Scientific Nicolet 6700 spectrometer. Absorption spectra were collected in diffuse reflectance mode using a shimadzu UV-3600 analyzer. The true density measurement was performed on an AccuPyc II 1340 gas densitometer. The chip resistance test was performed using the CHI760E electrochemical workstation. Capacitance-voltage (C-V) characteristics at different frequencies were measured using a K4200A-SCS parameter analyzer system and probe station equipment at room temperature and ambient conditions. The capacitance was tested for frequency and dielectric loss tangent curves at room temperature using an Agilent 4294A impedance analyzer, where the surface of the filtered a-CN film was directly connected to an Ag electrode. Nanoindentation test was performed using a nanoindenter G200XP nanoindenter with a surface approach speed of 10 nm/s.
Atomic Force Microscope (AFM): surface topography and peak force TUNA (PF-TUNA) measurements were tested using Bruker Dimension Icon AFM. AFM is provided withImaging and->Software 1.8. For PF-TUNA measurements, selected a-CN nanoplatelets were centrifuged at 2000r/min, 7000r/min were dispersed in ethanol to form a colorless dispersion, which was further dropped on Pt deposited Si/SiO with 5. Mu.L using electron beam deposition as a back gate 2 On the center of the wafer. The Pt substrate was electrically connected to the stainless steel disk with silver paint (as shown in fig. 11 a). The apparatus was heated at 120 ℃ for 2 hours in Ar atmosphere to remove the solvent before measurement. During the measurement, the disk is placed on an AFM platform (metal) and grounded. AFM tip coated with Bruker SCM-PIT-V2 platinum/iridium having a radius of 25nmThe terminal acts as a source gate to apply an external bias voltage. The topographical image of the sheet was measured using a common imaging tip (ScanAsyst air). During current imaging, a bias voltage of 1V was applied to obtain an electrically conductive pattern. For I-V characterization of points on the sample, a bias voltage of 5V was applied to the sample and the current was measured. The current is limited by the selected sensitivity range (2 nA/V). Therefore, all current measurements are limited to 2nA. All PF-TUNA measurements were performed in the PF-TUNA mode.
The embodiment provides an amorphous two-dimensional carbon nitride material (marked as a-CN) and a preparation method thereof, wherein in the embodiment, MAX phase Ti is adopted 3 AlCN is used as a raw material, and the specific preparation steps comprise:
MXene-Ti 3 CNT x is synthesized by the following steps: to 2g of Ti 3 AlCN powder was immersed in a mixture of 60ml 9M hydrochloric acid (HCl) and 4.8g lithium fluoride (LiF) and stirred by a magnetic rod at 35℃for 24 hours. The reaction mixture was filtered and washed with distilled water to bring the pH to approximately 6. The powder obtained was then redispersed in 100ml glass bottles and sonicated in an ice bath for 1 hour. Centrifuging the sonicated suspension at 3500rpm for 15min to collect a suspension containing a monolayer of at least MXene-Ti 3 CNT x Is a supernatant of (a) a supernatant of (b). Finally, the supernatant is freeze-dried under vacuum to obtain Ti 3 CNT x A powder;
synthesis of a-CN: 50mg of Ti 3 CNT x The powder was placed in an alumina crucible having a diameter of 10 mm. The filled alumina crucible and 1g of CuBr 2 The powder was sealed in a quartz tube (diameter 20mm, length 100 mm). The vacuum sealed tube was heated at 280 ℃ for 1 hour and then cooled to room temperature. The a-CN obtained was then treated with 5% HF for 24 hours to remove minute TiO formed during heating 2 . The product was then transferred to a 50ml polypropylene centrifuge tube and washed 3 times with distilled water. The precipitate was dispersed into 20mL of isopropyl alcohol (IPA) and sonicated for 1 hour. The a-CN was then collected by centrifuging the sonicated dispersion at 2000rpm for 5 minutes. Finally, the powder was freeze-dried under vacuum.
The embodiment also provides an a-CN film prepared by adopting a vacuum filtration method, and the more specific implementation steps comprise: the a-CN/IPA dispersion was filtered by vacuum (2000 rpm/min centrifugation) on a nylon membrane filter. The membrane filter was removed from the vacuum filter device and naturally dried before it was completely dried. The a-CN membrane was obtained by peeling from the membrane filter. The a-CN/IPA dispersion was filtered by vacuum (2000 rpm/min centrifugation) on an AAO template with a pore size of 200 nm. The filtered a-CN film was then transferred onto a Si substrate (about 500nm thickness, <0.005 Ω cm), and the film attached to the Si substrate was heated under Ar gas flow at 150 ℃ to remove solvent effect.
In a similar way, in MAX phase Ti 3 AlC 2 、Mo 2 Ga 2 C、Mo 2 Ti 2 AlC 3 Etching A atoms (Al/Ga) to obtain MXene-Ti 3 C 2 T x 、MXene-Mo 2 CT x MXene-Ti 3 C 2 Cl 2 And MXene-Mo 2 Ti 2 C 3 T x ；
MXene-Ti 3 C 2 Cl 2 Is synthesized by the following steps: 1g of Ti is weighed 3 AlC 2 MAX powder and 1g ZnCl 2 The powder was mixed uniformly in an agate mortar in an argon-filled glove box. The mixture was then transferred to an alumina crucible and heated in a quartz tube under Ar flow at 550 ℃ for 5h. After cooling, the reaction was washed with 1M HCl and deionized water to remove impurities.
a-C-Ti 3 C 2 T x And a-C-Ti 3 C 2 Cl 2 Is synthesized by the following steps: all conditions except the reaction temperature are the same as Ti 3 CNT x The conditions for synthesizing a-CN are the same; in this case, the reaction temperature is raised to 350℃because the Ti-C bond is stronger than the Ti-N bond; a-C-Mo 2 CT x And a-C-Mo 2 Ti 2 C 3 T x Also identical to a-CN, except that the reaction temperature was increased to 400 ℃. Notably, ti 3 CNT x And Ti is 3 C 2 T x With Br 2 The reaction of (2) can also be carried out under Ar flow in a quartz tube at the same temperature under vacuum condition at 100mg of MXene powder and 10g of CuBr 2 The powder was used as the reactant.
Obtaining a-C-Ti by adopting a similar film forming method 3 C 2 T x Film, a-C-Ti 3 C 2 Cl 2 Film, a-C-Mo 2 CT x And a-C-Mo 2 Ti 2 C 3 T x And (3) a film.
FIG. 1a illustrates a composition of Ti 3 AlCN to MXene-Ti 3 CNT x Then topologically converting into amorphous a-CN process diagram, MXene-Ti 3 CNT x Etching Ti from HF 3 Al atoms in AlCN, MXene-Ti 3 CNT x The topological conversion to a-CN occurs at 280 ℃ under bromine vapor generated by thermal decomposition of copper bromide in a sealed tube (equation 1). In the conversion process, MXene-Ti 3 CNT x The Ti atoms in the catalyst are gradually bromine etched to generate a gaseous product TiBr according to the equation (2) 4 After etching Ti atoms, MXene-Ti 3 CNT x The unsaturated carbon and nitrogen atoms in (a) will combine with each other to form an amorphous carbon nitride layer (a-CN), which changes color from dark purple to dark brown (fig. 2). Notably, the topological reaction can also be performed in an Ar flow at atmospheric pressure. The true density (referring to the actual mass per unit volume of solid matter in the absolute density state) of a-CN was measured by a true density analyzer to be 0.55g cm -3 Far lower than the parent MXene (0.9 g cm) -3 ) And amorphous material (1.0-2.3 gcm -3 )。
2CuBr 2 ＝2CuBr+Br 2 (G) (equation 1);
Ti 3 CNT x +Br 2 →TiBr 4 (G) +CN (Amorphos) (equation 2)
To get in depth to MXene-Ti 3 CNT x The topological transformation to a-CN was performed by X-ray diffraction (XRD) and Raman measurements, the results of which are shown in FIGS. 1b and c. FIG. 3 shows XRD patterns of the product at various etching times, it can be seen that MXene-Ti increases from 0 minutes to 30 minutes with conversion reaction time 3 CNT x Moving to a lower angle (from 7.5 DEG to 6.9 DEG), MXene-Ti 3 CNT x (004), (008) and (00)12 Other non-baseline peaks disappeared after 1 hour of reaction, the (002) peak disappeared, and a new broad peak of 20 ° to 30 ° appeared, indicating the formation of an amorphous structure (fig. 1 b). Furthermore, from the Raman spectrum, it was found that 1340cm was observed in the product of bromine etching for 1 hour -1 Broadband D band of (E) and-1571 cm -1 G band of (H), MXene-Ti 3 CNT x The EG band of (c) completely disappeared (fig. 1 c).
As can be seen from TEM pictures, a-CN has a two-dimensional morphology and has ultra-thin transparent features (fig. 4 a), the Selective Area Electron Diffraction (SAED) pattern shows a characteristic diffuse halo, confirming the amorphous structure of the product atomic layer (fig. 4 b), in sharp contrast to crystalline MXene with hexagonal diffraction pattern (fig. 5). The amorphous structure can be further verified by distortion corrected HRTEM images (spherical aberration electron microscopy), showing a random area (fig. 4c and d) without noticeable lattice fringes, similar to the reported amorphous material. STEM images and energy dispersive X-ray spectroscopy (EDS) elemental analysis measurements are shown in fig. 6, with a uniform distribution of C and N elements.
To further detect the local coordination environment of a-CN, near-edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS), raman spectroscopy, and fourier transform infrared spectroscopy (FTIR) were performed. In the C K-side spectrum of a-CN (FIG. 7 a), the broad characteristic resonance of σC-C/C-N occurs at 293eV, which is at g-C 3 N 4 This indicates that a significant number of C-C/C-N bonds are present in the prepared a-CN. In the nitrogen K edge region (FIG. 7 b), pyrrole N consisting of a single C-N bond shows a pronounced resonance at 400.1eV, which is shown at g-C 3 N 4 And is not present, indicating that C-N is at a high level in a-CN. Similarly, the generalized characteristic resonance of σN-C occurs at 407eV, also confirming the presence of a large number of C-N bonds in a-CN. The presence of C-C and C-N bonds can be further confirmed by C1s and N1s in high resolution XPS spectra, sp 3 The content of C was estimated to be 35.7%, expressed by sp 3 C-N (13.0%) and sp 3 C-C (22.7%) composition, which is given in g-C 3 N 4 Is not present (fig. 7c; fig. 8). Notably, three peaks of Ti2p, F1s and Clls disappeared in XPS measurement spectra, indicating MXene-Ti 3 CNT x The Ti atoms and surface functional groups thereon are completely removed during the topology conversion process (fig. 9). Raman spectroscopy further demonstrates sp 3 The presence of C-C/C-N (FIG. 7 d). In particular, I of a-CN D /I G 1.36, indicating an average defect distance in a-CN<2nm, lack of any long range order, further confirm its amorphous structure. FTIR spectrum (FIG. 7 e) shows that a-CN is at 1330cm -1 And-1608 cm -1 Characteristic vibration peaks of C-N and c=n were present at the positions, and Ti was not shown 3 CNT x Ti-O peak in (2) and g-C including characteristic peak of s-triazine 3 N 4 In contrast, a-CN was shown to have a large number of C-N bonds, consistent with the N K side of C1s and XPS analysis results.
In addition, amorphous atomic layers can be easily assembled into a large-area thin film (fig. 10). The film resistance of a-CN was 1.08X10 10 Omega/≡, compared with Ti 3 CNT x The film was 8 orders of magnitude higher (40.7Ω/≡) and was close to the reported nitrogen-induced amorphous carbon (-2.5X10) 10 Ωcm -1 ) Discloses the following conductive Ti after topology conversion reaction 3 CNT x Complete transition to insulation a-CN; in contrast, a-C-Ti 3 C 2 T x Is 343mΩ/≡which is attributable to the larger I D /I G Value (2.4) (fig. 3 f).
To evaluate the dielectric properties of the prepared materials, a-CN nanoplatelets were coated on Pt-deposited SiO 2 Conducting AFM measurements on wafers as shown in FIGS. 11 a-11 b, 12 and 13, the resulting current-voltage (I-V) curves show that for a-CN nanoplatelets (3.8 nm and 4.2 nm) and a-CN films (-310 nm), the current increases sharply (Poole-Frenkel tunneling) over the voltage range of about 2-3V and 165-180V, respectively, the corresponding critical field strengths calculated from the ratio of critical voltage to thickness are about 6.6.+ -. 0.8MV cm, respectively -1 And 5.6.+ -. 0.2MV cm -1 Near the reported amorphous boron carbide film (7.3 MV cm -1 ) This is the highest value reported for materials with dielectric constants less than 2. This slow decrease in breakdown strength should result from space charge formation and kinetics as a-CN increases from 4.2nm to 310nm, which is similar to the reported SrTiO 3 And a polyethylene film. And does not haveThe current is significantly enhanced compared to the area of the sample, saturating with the minimum bias voltage. The direct optical bandgap of 1.45eV calculated from the absorption spectrum can also confirm the insulating properties (fig. 11 c). The capacitance of the a-CN film with a thickness of-310 nm shows a small value at 100 kHz-0.24 pF, greater than that of air (-0.05 pF), and the capacitance decreases slightly to-0.2 pF as the frequency increases from 100kHz to 1MHz, similar to that of the a-BN reported. The impedance analyzer was further used to calculate the dielectric constants of a-CN films with thicknesses of-310 nm and 25 μm (FIG. 11 d), which were approximately 1.69.+ -. 0.01 (310 nm) and 1.62.+ -. 0.01 (25 μm), respectively, at 100kHz frequencies, well below the reported g-C 3 N 4 62 and still lower than other amorphous films and other low dielectric materials reported. Dielectric loss means the energy consumption by converting electrical energy into heat, dielectric loss is lower than 0.03, much lower than SiO, for a 25 μm thick a-CN film without a substrate, in the frequency range of 100kHz to 100MHz 2 And (0.07), indicating lower energy loss if the a-CN film is used in an integrated circuit. Such low dielectric constants and dielectric losses can be attributed to the advantageous structure and characteristics of the a-CN: 1) And sp (sp) 3 C analysis correlation, sp in amorphous phase with localized electrons 3 The high level of C reduces electron polarization, effectively reducing dielectric constant; 2) 0.55g cm -3 The very low density of (2) introduces a large number of voids and vacancies of dielectric constant 1, significantly reducing the dielectric constant of a-CN.
To further evaluate the hardness and Young's modulus of the a-CN film, nanorecognition measurements were performed at a surface approach speed of 10 nm/s. The a-CN film had a hardness of about 0.12GPa, approaching that of porous SiCOH (0.28 GPa), but lower than that of commercial SiO 2 Hardness (10-12 GPa). The young's modulus of a-CN films is about 2GPa, which cannot meet the current chemical mechanical polishing requirements of dielectric materials with young's modulus as high as 8GPa, but is advantageous for flexible electronics. Through further densification, a-CN films may be used in current integrated circuits.
In summary, the present invention prepares amorphous two-dimensional amorphous carbon nitride materials by topologic transformation of MXene containing carbon and nitrogen in the X-position under bromine vapor. The a-CN obtained had a concentration of 0.55g cm -3 Is very low in density and high in sp of 35.7% 3 C level. Thus, on our assembled a-CN film, an ultra low dielectric constant of 1.69, lower than reported amorphous films and other low dielectric materials (1.8-4), was achieved at 100 kHz. In addition, the breakdown strength of the assembled a-CN film reaches 5.6MV cm -1 Meets the application requirements. Our results indicate that amorphous two-dimensional carbon nitride atomic layers with excellent low-k dielectric properties are likely to be applied in future nanoelectronics.
It should be noted that, MXene is a precursor for synthesizing two-dimensional amorphous carbon nitride material according to the present invention, MXene is a two-dimensional material with similar structure, in other embodiments, MXene as a precursor may also be MXene composed of different elements, and represented by chemical formula M n+1 X n T x Wherein M is selected from one or more of transition metal elements; x is selected from carbon and nitrogen, T represents a functional group including-F, -Cl, br, I, -O, -S, -OH, NH 4 One or more of the following; n is more than or equal to 1 and less than or equal to 4. Similarly, MAX phase materials as MXene precursors are also a class of ceramic materials, represented by the chemical formula M n+1 AX n In other embodiments, M is selected from one or more of the transition metal elements; a is a metal element selected from the third main group and/or the fourth main group; x is selected from carbon and nitrogen; n is more than or equal to 1 and less than or equal to 4. In another embodiment, the MAX phase is selected from Ti 2 AlC 0.5 N 0.5 、Nb 3 AlCN、Mo 3 GaCN、Ti 3 SnCN、V 3 AlC 0.8 N 0.2 And the like, and the amorphous two-dimensional carbon nitride material can be obtained by adjusting etching conditions.
In other embodiments, cuBr 2 Can also be replaced by other metal bromide, and can decompose Br under heating 2 Such as FeBr 3 Etc.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.

Claims (10)

1. A carbon nitride material, wherein the carbon nitride material has a two-dimensional morphology and an amorphous structure.
2. The carbon nitride material according to claim 1, wherein the carbon nitride material has a thickness of 5nm or less.
3. The carbon nitride material of claim 1, wherein XPS testing of the carbon nitride material reveals that the material comprises sp 3 Hybrid C-N bond and sp 2 A hybrid C-N bond;
and/or, the spherical aberration electron microscope diffraction image of the carbon nitride material has no diffraction spots;
and/or, the spherical aberration electron microscope image of the carbon nitride material shows no lattice stripes;
and/or the XRD spectrum of the carbon nitride material has dispersed diffraction peaks between 20 and 30 degrees.
4. A carbon nitride material according to any one of claims 1 to 3, wherein the carbon nitride material has a dielectric constant of 2 or less;
and/or the density of the carbon nitride material is less than or equal to 1g/cm 3 。
5. A method for producing a carbon nitride material according to any one of claims 1 to 4, comprising the steps of:
etching the A component in the MAX phase material by adopting a first etchant to obtain an MXene material;
mixing the MXene material with a second etchant metal bromide and/or bromine gas, and sintering at a preset temperature to obtain a carbon nitride material;
the MAX phase material consists of M, A and X elements, M is one or more of transition metal elements, A is selected from metal elements of a third main group or a fourth main group, and X is carbon and nitrogen.
6. The method of claim 5, wherein the first etchant is HF, HCl, HBr, HI, I 2 One or more of fluoride salt + hydrochloric acid, metal halide salt; preferably, the first etchant is HF, fluoride salt+hydrochloric acid or HCl;
and/or, the temperature of the second etchant for etching is 280-1000 ℃;
and/or the etching time of the second etching agent is more than or equal to 60 minutes.
7. A film comprising the carbon nitride material according to any one of claims 1 to 4, or the carbon nitride material obtained by the production method according to claim 5 or 6;
or, consist of the carbon nitride material according to any one of claims 1 to 4, or the carbon nitride material obtained by the production method according to claim 5 or 6.
8. The film of claim 7, wherein the film has a dielectric constant of 2 or less;
and/or the breakdown strength of the film is more than or equal to 5MV cm -1 ；
And/or the film is an insulating material;
and/or the thickness of the film is more than or equal to 3nm; preferably, the thickness is between 3nm and 100 μm; and still more preferably between 3nm and 25 μm.
9. An electronic device comprising the carbon nitride material according to any one of claims 1 to 4;
or, the carbon nitride material obtained by the production method according to claim 5 or 6;
or, the film of claim 7 or 8;
preferably, the electronic device has flexibility.
10. An integrated circuit or communication device comprising a carbon nitride material according to any one of claims 1 to 4; or, the film of claim 7 or 8; or, an electronic device as claimed in claim 9.
CN202310777120.1A 2023-06-28 2023-06-28 Two-dimensional amorphous carbon nitride material, preparation method thereof, film and electronic device Pending CN116969425A (en)

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