Infrared radiation detectors using carbon nanotubes-silicon vanadium oxide and or amorphous silicon nanoparticles-CNT nanocomposites and methods of constructing the same
09677946 ยท 2017-06-13
Assignee
Inventors
Cpc classification
G01J5/0853
PHYSICS
International classification
H01L31/028
ELECTRICITY
H01L31/09
ELECTRICITY
Abstract
The present disclosure relates to microbolometer structures having top layers of amorphous silicon or vanadium oxide. In some examples, combinations of carbon nanotubes, nanoparticles, and/or thin films can be deposited atop the existing top layer of amorphous silicon or top layer of vanadium oxide of a microbolometer structure. Such configurations can increase the sensitivity of the microbolometers to less than 4 mK, less than 2 mK, and in some examples less than 1 mK.
Claims
1. An Infrared (IR) detector comprising: a substrate; a film of vanadium oxide or amorphous silicon suspended over the substrate and between electrical contacts; a film of silicon CNT nanocomposite on top of the thin film of vanadium oxide or amorphous silicon, the thin film of CNT nanocomposite comprising nanoparticles dispersed within aligned carbon nanotubes at approximately 0.05% to 10% by volume; first and second conductive contacts in electrical communication with the thin film of vanadium oxide or amorphous silicon of Silicon-CNT or Si-CNT nanocomposites; a non-continuous film disposed on top of the substrate comprising at least one of silicon nitride or amorphous silicon.
2. The IR detector of claim 1 wherein the a film of silicon CNT nanocomposite is composed of single wall or multi-wall carbon nanotubes having diameters corresponding to a tuned IR response wavelength.
3. The IR detector of claim 1 wherein the film of silicon CNT nanocomposite is composed of multi wall carbon nanotubes having diameters corresponding to a tuned IR response wavelength.
4. The IR detector of claim 1 wherein the a film of silicon CNT nanocomposite is composed of single wall carbon nanotubes and multi wall carbon nanotubes having diameters corresponding to a tuned IR responsive wavelength.
5. The IR detector of claim 1 wherein the detector exhibits an NEDT of <1 mk and a noise floor of 0.05 mV RMS.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) The invention description below refers to the accompanying drawings, of which:
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DETAILED DESCRIPTION
(11) The present disclosure relates to microbolometer structures having top layers of amorphous silicon or vanadium oxide. In some examples, combinations of carbon nanotubes, nanoparticles, and/or thin films can be deposited atop the existing top layer of amorphous silicon or top layer of vanadium oxide of a microbolometer structure. Such configurations can increase the sensitivity of the microbolometers to less than 4 mK, less than 2 mK, and in some examples less than 1 mK.
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(13) The carbon nanotubes 1 can include nanoparticles 2 dispersed or mixed therewith to form a dispersion solution of carbon nanotubes 1 and nanoparticles 2, also referred to herein as a nanocomposite. The nanoparticles 2 can include any type of nanoparticles, such as one or more of silicon nanoparticles and/or vanadium oxide nanoparticles. The nanoparticles 2 can be dispersed within the dispersion solution approximately 0.05% to 10% by volume (e.g., +/0.05%), with the carbon nanotubes 1 making up the remaining volume of the dispersion solution. The nanoparticles 2 can also be deposited within the layer 3, forming a composite layer of -silicon or vanadium oxide and silicon nanoparticles or vanadium oxide nanoparticles, in any combination. Such combinations can include, for example a layer of -silicon and silicon nanoparticles, a layer of -silicon and vanadium oxide nanoparticles, a layer of vanadium oxide and silicon nanoparticles, or a layer of vanadium oxide and vanadium oxide nanoparticles.
(14) During fabrication of the example of
(15) In the example of
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(17) The carbon nanotubes 4 can include nanoparticles 2 dispersed or mixed therewith to form a dispersion solution of carbon nanotubes 1 and nanoparticles 2. The nanoparticles 2 can include any type of nanoparticles, such as one or more of silicon nanoparticles and/or vanadium oxide nanoparticles. The nanoparticles 2 can be dispersed within the dispersion solution approximately 0.05% to 10% by volume (e.g., +/0.05%), with the carbon nanotubes 4 making up the remaining volume of the dispersion solution. The nanoparticles 2 can also be deposited within the layer 3, forming a composite layer of -silicon or vanadium oxide and silicon nanoparticles or vanadium oxide nanoparticles, in any combination. Such combinations can include, for example a layer of -silicon and silicon nanoparticles, a layer of -silicon and vanadium oxide nanoparticles, a layer of vanadium oxide and silicon nanoparticles, or a layer of vanadium oxide and vanadium oxide nanoparticles.
(18) During fabrication of the example of
(19) In the example of
(20)
(21) The carbon nanotubes 5 can include nanoparticles 2 dispersed or mixed therewith to form a dispersion solution of carbon nanotubes 5 and nanoparticles 2. The nanoparticles 2 can include any type of nanoparticles, such as one or more of silicon nanoparticles and/or vanadium oxide nanoparticles. The nanoparticles 2 can be dispersed within the dispersion solution approximately 0.05% to 10% by volume (e.g., +/0.05%), with the carbon nanotubes 5 making up the remaining volume of the dispersion solution. The nanoparticles 2 can also be deposited within the layer 3, forming a composite layer of -silicon or vanadium oxide and silicon nanoparticles or vanadium oxide nanoparticles, in any combination. Such combinations can include, for example a layer of -silicon and silicon nanoparticles, a layer of -silicon and vanadium oxide nanoparticles, a layer of vanadium oxide and silicon nanoparticles, or a layer of vanadium oxide and vanadium oxide nanoparticles.
(22) In this example, a thin non-continuous film 6 can be deposited on the layer 3. The film 6 can have a thickness (e.g., height above a surface of the layer 3) of less than five angstroms and can be formed of any material having low stiction properties and a low Van der Waals force. In one example, the film can include at least one of a silicon nitride (Si.sub.3N.sub.4) film and/or an amorphous silicon film. The film 6 can comprise a nonuniform distribution of islands atop the layer 3 at nonuniform intervals.
(23) During fabrication, the film 6 can be deposited using chemical vapor deposition. As described above, the dispersion solution, including a mixture of carbon nanotubes and nanoparticles (vanadium oxide or silicon) is deposited at regions where the film is not deposited atop the layer 3. In areas where the film 6 does not contact the layer 3 (e.g., a space defined between adjacent islands of film 6), the nanoparticles adhere to the layer 3. However, at areas with the film 6 contacts the layer 3, the nanoparticles do not adhere to the layer 3. Moreover, the nanoparticles and carbon nanotubes do not adhere to any portion of the film 6, thereby creating a gap between the film 6 and the nanotube/nanoparticle mixture. This configuration, which can be described as stripes in the detector surface, can increase modulation transfer function and overall efficiency of the detector.
(24) In the example of
(25) One advantage of the present disclosure is that the use of Silicon or vanadium oxide nanoparticles dispersed within a carbon nanotube matrix provides increased optical electrical and thermal conductivity beyond the existing -Silicon or vanadium oxide films, which will result in a wider range in sensitivity. Combining the -silicon and/or vanadium oxide film with a CNT nanocomposite results in increased sensitivity due to minimization of the noise floor. Although described above, such improved sensitivity can be summarized in the following table:
(26) TABLE-US-00001 FIG. 1A FIG. 1B FIG. 1C NEDT of <4 mK NEDT of <2 mK NEDT of <1 mK Noise floor Noise floor Noise floor 0.1 mV RMS 0.1 mV RMS 0.05 mV RMS
(27) As will be described in greater detail below, examples of
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(29) Due to the mechanical properties of the microbolometer structure and in order not to modify the underlying CMOS circuit performance, the next steps for the three proposed embodiments must not surpass 150 degrees C. or use etch chemistries that are incompatible with the underlying structure. Such incompatible etch chemistries include chemistries including carbon of any kind, as the use of carbon could result in carbon entering the cavity 111, which could render the detector structure inoperable.
(30) At
(31) At
(32) At
(33) At
(34) At
(35) At
(36) According to the illustrative embodiment, light detecting elements can have a suspended region 112 overlying a gap 111, above substrate material 101. The gap is created using techniques as described herein. Second substrate material 102 may be an insulator such as one listed above and may be the same insulating material as 102 or second substrate material 101 may be a semiconductor (such as, but not limited to, Si (single crystal, polycrystalline and amorphous), Ge, SiGe, SiC, Diamond, GaN, GaAs, GaP, AlGaAs, InP, GaP, CdTe, AlN, InAs, AlxInl-xP, and other III-V and II-VI semiconductors) or a conductor (such as, but not limited to, Al, Cu, W, Al(<1% Cu), Co, Ti, Ta, W, Ni, Mo, Pd, Pt, TiW, Ru, CoSix, WSi2, TiSix, TaN, TiN, TiAlN, RuN, RuO, PtSi, Pd2Si, MoSi2, NiSix). The substrate material systems can be chosen for circuitry technologies considerations. The suspended region of nanostructure 112 defines the electromagnetic sensing region of the detecting element. The light detection from the detecting element is controlled by driving circuitry depicted in
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(40) In fabrication of the examples of
(41) At block 306, using a set of carbon nanotubes both single and multiwall configurations, suspend carbon nanotubes in either aqueous or non-aqueous casting solvents. Wafer is placed on a rotating chuck and rotated at 10-500 rpm depending on thickness and CNT casting solvent solution is sprayed on wafer resulting in a film of nanotubes.
(42) At block 307, for the random (unaligned) carbon nanotubes, deposit random nanotubes in casting solvent, shake well to disperse in solution.
(43) At block 308, after creating the nanotube films described above, using a high voltage field coupled to the wafer aligning or partially aligning carbon nanotubes after applying a high voltage field. (50-250V). This is tunable depending on the voltage level and application duration.
(44) In fabrication of the examples of
(45) At block 310, deposit silicon nanoparticles in spray deposit 0.01 to 10% by volume. Rotate the wafer from 10-500 rpm and apply to wafer. Random CNT film will spread over the wafer surface uniformly.
(46) At block 311, deposit silicon nanoparticles in spray deposit 0.01 to 10% by volume. Rotate the wafer from 10-500 rpm and apply to wafer. Random CNT film will spread over the wafer surface.
(47) At block 312, after creating the nanotube films described above, using a high voltage field coupled to the wafer aligning or partially aligning the carbon nanotubes after applying a high voltage field. (50-250V). This alignment is tunable depending on the voltage level and application duration.
(48) In fabrication of the example of
(49) At block 313, using DC Sputtering or e-beam evaporation, deposit a non-continuous thin film of either Si3N4 or SiO2 on the wafer surface. The deposition of films without features is dependent on the deposition time, where the island coalesce into a continuous film. In the case where features such as stripes are required, a molybdenum mask with the appropriate features is fabricated. The deposition is then conducted through the mask and the features are deposited on wafer.
(50) At block 314, using either an aqueous or non-aqueous solution the nanoparticles are suspended in the casting solvent. The concentration of silicon nanoparticles in the casting solvent is 0.01 to 10% by volume. The wafer is rotated at 10-100 RPM and the nanoparticles/casting solvent is sprayed on during rotation creating a uniform dispersion of nanoparticles across the wafer.
(51) At block 315, after creating the nanotube films described above, using a high voltage field coupled to the wafer aligning or partially aligning carbon nanotubes after applying a high voltage field. (50-250V). This is tunable depending on the voltage level and application duration.
(52) At block 316, for the random case, deposit random nanotubes in casting solvent, shake well to disperse in solution.
(53) Each of the flow processes A-C above continue with blocks 309, 317, and 318 in fabricating the microbolometer structure.
(54) At block 309, to ensure attachment of the nanoparticles to the CNTs a H2 or Cl2 glow discharge etch is undertaken. In a vacuum system a circular copper coil is coupled to a RF power supply and after achieving base pressure of less the 5 microns, either H2 or Cl2 is flowed in 1-15 sccm flows. The discharge is ignited and the surface of the nanotubes are etched resulting in dangling carbon bonds which the nanoparticles will attach themselves to.
(55) At block 317, after creating the nanotube films described above, using a high voltage field coupled to the wafer aligned or partially align carbon nanotubes after applying a high voltage field. (50-250V). This is tunable depending on the voltage level and application duration. Using either an aqueous or non-aqueous solution the nanoparticles are suspended in the casting solvent. The concentration of silicon nanoparticles in the casting solvent is 0.01 to 10% by volume. The wafer is rotated at 10-100 RPM and the nanoparticles/casting solvent is sprayed on during rotation creating a uniform dispersion of nanoparticles across the wafer.
(56) At block 318, using either argon or H2 in N2 at 2% by volume put wafers in an oven at 50-150 degree Celsius and anneal for 1 to 60 minutes to obtain a stable nanostructure.
(57) Upon deposition of the carbon nanotube and nanoparticle composite upon the amorphous silicon layer 304, the microbolometer can detect incident infrared radiation 301.
(58)
(59) In fabrication of the example of
(60) At block 310, using a set of carbon nanotubes both single and multiwall configurations. Suspend nanotubes carbon nanotubes in either aqueous or non-aqueous casting solvent. Wafer is placed on a rotating chuck and rotated at 10-500 rpm depending on thickness and CNT casting solvent is sprayed on wafer resulting in a film of nanotubes.
(61) At block 311, after creating the nanotube films described above, using a high voltage field coupled to the wafer aligned carbon nanotubes after applying a high voltage field. (50-250V). The degree of alignment is tunable depending on the voltage level and application duration.
(62) At block 312, After the high voltage alignment, use a nitrogen environment for one hour to drive off moisture that might have coated the nanotubes during the high voltage alignment.
(63) At block 313, for the random case, deposit random nanotubes in casting solvent, shake well to disperse in solution.
(64) At block 314, to insure attachment of the nanoparticles to the CNTs a H2 or Cl2 glow discharge etch is undertaken. In a vacuum system a circular copper coil is coupled to a RF power supply and after achieving base pressure of less the 5 microns, either H2 or Cl2 is flowed in 1-15 sccm flows. The discharge is ignited and the surface of the nanotubes are etched resulting in dangling carbon bond which the nanoparticles will attach themselves to.
(65) At block 315, using either an aqueous or non-aqueous solution the nanoparticles are suspended in the casting solvent. The concentration of silicon nanoparticles in the casting solvent is 0.01 to 10% by volume. The wafer is rotated at 10-100 RPM and the nanoparticles/casting solvent is sprayed on during rotation creating a uniform dispersion of nanoparticles across the wafer.
(66) At block 330, using either argon or H2 in N2 at 2% by volume put wafers in a oven at 50-150 degree Celsius and anneal for 1 to 60 minutes to obtain a stable nanostructure.
(67) In fabrication of the example of
(68) At block 316, using a tube furnace at 150 C 10-50 sccm flow Argon, process the wafers for one hour to drive off h20 absorbed from previous processing.
(69) At block 317, using either an aqueous or non-aqueous solution the nanoparticles are suspended in the casting solvent. The concentration of silicon nanoparticles in the casting solvent is 0.01 to 10% by volume. The wafer is rotated at 10-100 RPM and the nanoparticles/casting solvent is sprayed on during rotation creating a uniform dispersion of nanoparticles across the wafer.
(70) At block 318, after creating the nanotube films described above, using a high voltage field coupled to the wafer aligned or partially align carbon nanotubes after applying a high voltage field. (50-250V). The degree of alignment is tunable depending on the voltage level and application duration
(71) At block 319, for random tubes utilize an adhesion promoter to insure stickiness to the underlying material. The Compound is HMDS (hexamethyldisalizane) in Freon vapor is used here.
(72) At block 320, for the random case, deposit random nanotubes in casting solvent, shake well to disperse in solution.
(73) At block 321, to insure attachment of the nanoparticles to the CNTs a H2 or Cl2 glow discharge etch is undertaken. In a vacuum system a circular copper coil is coupled to a RF power supply and after achieving base pressure of less the 5 microns, either H2 or Cl2 is flowed in 1-15 sccm flows. The discharge is ignited and the surface of the nanotubes are etched resulting in dangling carbon bond which the nanoparticles will attach themselves to.
(74) The process then continues with blocks 315 and 330, as described above.
(75) In fabrication of the example of
(76) At block 322, using DC Sputtering or e-beam evaporation deposit on non-continuous thin films of Si3N4 or SiO2 on the wafer surface. The deposition of films without features is dependent on the deposition time, where the island coalesce into a continuous film. In the case where features such as stripes are required a molybdenum mask with the appropriate features is fabricated. The deposition is then conducted through the mask and the features are deposited on wafer
(77) At block 323, using either an aqueous or non-aqueous solution the nanoparticles are suspended in the casting solvent. The concentration of silicon nanoparticles in the casting solvent is 0.01 to 10% by volume. The wafer is rotated at 10-100 RPM and the nanoparticles/casting solvent is sprayed on during rotation creating a uniform dispersion of nanoparticles across the wafer.
(78) At block 324, after creating the nanotube films described above, using a high voltage field coupled to the wafer aligned or partially align carbon nanotubes after applying a high voltage field. (50-250V). The degree of alignment is tunable depending on the voltage level and application duration.
(79) At block 325, using a set of carbon nanotubes both single and multiwall configurations. Suspend nanotubes carbon nanotubes in either aqueous or non-aqueous casting solvent. Wafer is placed on a rotating chuck and rotated at 10-500 rpm depending on thickness and CNT casting solvent is sprayed on wafer resulting in a film of nanotubes.
(80) At block 326, to insure attachment of the nanoparticles to the CNTs a H2 or Cl2 glow discharge etch is undertaken. In a vacuum system a circular copper coil is coupled to a RF power supply and after achieving base pressure of less the 5 microns, either H2 or Cl2 is flowed in 1-15 sccm flows. The discharge is ignited and the surface of the nanotubes are etched resulting in dangling carbon bond which the nanoparticles will attach themselves to.
(81) At block 327, using either argon or H2 in N2 at 2% by volume put wafers in a oven at 50-150 degree Celsius and anneal for 1 to 60 minutes to obtain a stable nanostructure.
(82) Upon deposition of the carbon nanotube and nanoparticle composite upon the VOx layer 304, the microbolometer can detect incident infrared radiation 301.
(83)
(84) The foregoing has been a detailed description of illustrative embodiments of the invention. Various modifications and additions can be made without departing from the spirit and scope of this invention. Features of each of the various embodiments described above may be combined with features of other described embodiments as appropriate in order to provide a multiplicity of feature combinations in associated new embodiments. Furthermore, while the foregoing describes a number of separate embodiments of the apparatus and method of the present invention, what has been described herein is merely illustrative of the application of the principles of the present invention. Accordingly, this description is meant to be taken only by way of example, and not to otherwise limit the scope of this invention.