Adjacent electrode which provides pixel delineation for monolithic integration of a colloidal quantum dot photodetector film with a readout integrated circuit
11528442 · 2022-12-13
Assignee
Inventors
- Richard Edward Pimpinella (Naperville, IL, US)
- Anthony Joseph Ciani (Palatine, IL, US)
- Christoph H. Grein (Wheaton, IL, US)
Cpc classification
H01L31/09
ELECTRICITY
H04N25/77
ELECTRICITY
H01L27/14683
ELECTRICITY
H04N25/75
ELECTRICITY
International classification
H01L31/0352
ELECTRICITY
Abstract
A photodetector device is provided that includes a ROIC having a top surface with a plurality of electrically conductive first electrodes within a pattern of surface areas on the top surface each surface area having a border, and an electrically conductive electrode grid having a portion on the border of each of the surface areas; and a photodetector film overlying the surface area. The electrode grid can be configured to surround each surface area to define the borders of the surface areas as pixels. The photodetector film can be a colloidal quantum dot film. The ROIC has circuit elements signal-connected to the plurality of first electrodes. Methods for forming the photodetector device include photolithography and deposition methods.
Claims
1. A method of making a photodetector device, comprising the steps of: providing a substrate with a plurality of electrically-conducting first electrodes arranged in a pattern; applying a photoresist layer on said substrate, covering the first electrodes; applying a photolithography mask to the photoresist layer defining exposed areas and non-exposed areas; exposing the photoresist and the mask to electromagnetic radiation; removing one of the exposed areas and non-exposed areas of photoresist to define a pattern of removed photoresist areas and remaining photoresist areas; applying a layer of electrically conductive material to at least the removed photoresist areas to form an electrode grid of electrically conductive material; removing the remaining photoresist areas; and applying a photodetector film onto the substrate and onto the grid of electrically conductive material.
2. The method according to claim 1, wherein the step of applying a photodetector film is further defined in that the film comprises colloidal quantum dots.
3. The method according to claim 1 wherein the step of providing a substrate is further defined in that the substrate is an ROIC having circuit elements signal-connected to said plurality of first electrodes.
4. The method according to claim 1, wherein said step of exposing the photoresist and the mask to electromagnetic radiation is further defined in that said electromagnetic radiation is UV radiation.
5. A method of making a photodetector device, comprising the steps of: providing a substrate with a plurality of electrically-conducting first electrodes arranged in a pattern; applying a layer of electrically conductive material to the substrate covering the plurality of electrically conductive first electrodes; applying a photoresist layer on said layer of electrically conductive material; applying a photolithography mask to the photoresist layer defining exposed areas and non-exposed areas; exposing the photoresist and the mask to electromagnetic radiation; removing one of the exposed areas and non-exposed areas of photoresist to define a grid of photoresist and removed photoresist areas; removing the layer of electrically conductive material in the areas exposed by the removed photoresist areas while maintaining said first electrodes; and applying a photodetector film onto the substrate and onto the grid of electrically conductive material.
6. The method according to claim 5, wherein after the step of removing the layer of electrically conductive material in the areas exposed by the removed photoresist areas, and before the step of applying a photodetector film onto the substrate and onto the grid of electrically conductive material, performing the step of removing the grid of photoresist to expose a grid of electrically conductive material.
7. The method according to claim 5, wherein the step of applying a photodetector film is further defined in that the film comprises colloidal quantum dots.
8. The method according to claim 5 wherein the step of providing a substrate is further defined in that the substrate is an ROIC having circuit elements signal-connected to said plurality of first electrodes.
9. The method according to claim 5, wherein said step of exposing the photoresist and the mask to electromagnetic radiation is further defined in that said electromagnetic radiation is UV radiation.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
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DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
(27) While this invention is susceptible of embodiment in many different forms, there are shown in the drawings, and will be described herein in detail, specific embodiments thereof with the understanding that the present disclosure is to be considered as an exemplification of the principles of the invention and is not intended to limit the invention to the specific embodiments illustrated.
(28) Exemplary methods according to the invention provide for an adjacent “electrode” or “contact” for an array of photodetectors, and for the fabrication of the array of photodetectors upon a host ROIC. This adjacent electrode could be formed in a variety of ways using present day techniques, or new techniques as of yet unforeseen. The exemplary methods are described in
(29) Referring first to
(30) The plurality of pixel electrodes 32 are arranged spaced apart in a repeating pattern, with one pixel electrode at each pixel location. Proper electrical voltage biasing of the photodetector film, such as a CQD film, requires two electrodes, the electrodes 32 provides the first electrode and the electrode grid 60 provides the second electrode. This grid 60 should not intersect any electrode 32 on the ROIC, or the CQD film in that region will not be under an electrical voltage bias. This electrode grid 60 can be in contact with the ROIC's common contact 36 located around the edge of the ROIC 30, to provide proper functionality with the ROIC.
(31) The photodetector film 70 may be composed of a variety of chemical compounds or elements. The photodetector film may be of suitable size to absorb at the chosen wavelength of electromagnetic radiation. The film may be formed across the entire wafer of the ROIC, part of such wafer, on an isolated ROIC or on an ROIC already mounted to its carrier. The film 70 may be masked to cover only a portion of the available active area of the imaging array. The film 70 may be removed from areas of the ROIC 30 post-deposition to assure such electrical isolation if desired.
(32) The electrode grid 60 separates each area of the CQD film 70 into areas in which intercepted photons near each pixel electrode 32 of the ROIC will generate an electrical signal in that proximity, and such current will flow between the pixel electrode 32 and the electrode grid 60 at the pixel site. The grid provides direct pixel definition of the CQD film without etching or post-deposition processing. The probability that a photon intercepted at one delineated pixel site has its related electrical signal detected at another pixel site (known as cross-talk) is also greatly diminished. This is because any such photon-generated signal current must now transit through the CQD film 70 in opposition to the applied voltage bias of the desired pixel in order to be instead detected at the adjacent pixel.
(33) Such a grid 60 may be formed from any electrically conductive substance, such as metals, metal alloys, or any material or combination of materials with a high electron or hole mobility. The common grid may be composed of a conducting material such as gold, copper, aluminum, titanium, indium tin oxide, or any other conducting compound or element or combination thereof that can be deposited onto the host ROIC. The conducting material shall have conductivity sufficient to carry the electrical signals of the detector array when deposited.
(34) With the newly prepared ROIC 30 with the photodetector CQD film 70 deposited thereon, the formation into a focal plane array (“FPA”) may take place. This method will provide electrical interfacing between the ROIC and external frame-grabbing hardware and the integration of the optical pathway into a full camera system.
Example 1
(35) One such process to fabricate an adjacent electrode grid in preparation for a photodetector film is described below. This method will be broken into 3 primary steps each with listed sub-steps: 1) definition of electrode areas via photolithography, 2) development of electrode areas via developer solution, 3) deposition of a conductive layer and subsequent removal of excess photoresist. It is preferred that listed steps be performed in an ISO Class 10/100 or superior clean room environment.
(36) Step 1: Definition of Electrode Areas Via Photolithography
(37) 1.1 An ROIC 30 is provided as a starting workpiece, configured as shown in
(38) 1.2 Next, as shown in
(39) 1.3 Next, this ROIC 30 with photoresist 50 can be given a short term thermal anneal at or near 145° C. at or near a 60 second duration, otherwise known as a ‘soft bake’. Other temperatures or durations which prepare the photoresist for light exposure will also be suitable.
(40) 1.4 As described in
(41) 1.5 After alignment on the top surface of the photoresist on the ROIC 30, the photolithography mask is placed in close proximity to an ultraviolet light source.
(42) 1.6 The photoresist 50 is exposed to ultraviolet light for a duration at or near 30 seconds. Depending on the choice for photoresist, other such treatments may be applied at this time which prepare the photoresist for subsequent removal and definition. For example, for a negative photoresist, UV exposure for 30 seconds will strengthen the polymers exposed, such as in the square areas 52, allowing the unexposed areas square grid areas 56 to be safely removed in subsequent steps.
(43) 1.7 After exposure, the host ROIC 30 and photoresist 50 are given a second thermal anneal, now at a temperature at or near 100° C. and at or near 60 second duration, known as a “hard bake.” Any other preparation process suitable for the chosen photoresist will be performed at this time which prepares the photoresist to be removed in subsequent steps.
(44) Step 2: Development of Electrode Areas Via Developer Solution.
(45) 2.1 The prepared host ROIC from Step 1 is immersed completely in a suitable development solution such as RD6 for a duration at or near 60 seconds or until such time as the photoresist is fully developed. As shown in
(46) 2.2 Two pure de-ionized water solutions are prepared, and the host ROIC is immersed within the first solution and possibly lightly agitated. Then it is transferred to the second de-ionized water solution and again lightly agitated, providing a cleaning process.
(47) 2.3 After cleaning, the host ROIC is dried through flowing gaseous nitrogen of suitable purity to avoid contamination. Any such process to remove unwanted and excess water may be used here providing that the host ROIC is not damaged, nor the defined areas from previous steps removed.
(48) 2.4 The host ROIC is now optionally inspected for damage and proper exposure. It is at this stage combinations of any previous steps may be performed following any re-processing or chemical etching to removed unwanted areas. For example, if unexposed areas 56 appear to not have had a long enough duration to properly define the electrode grid, the photoresist may be removed through a method as in step 1.1 and subsequent steps from 1.2 to 2.3 may be performed again.
(49) Step 3: Deposition of a Conductive Layer and Subsequent Removal of Excess Photoresist
(50) 3.1 As shown in
(51) 3.2 After deposition of the conducting layer 58, the remaining photoresist 52 and portions of the conducting layer 58 located on the photoresist 52, are removed as shown in
(52) Step 4: Deposition of a Photodetector Film, Such as One Comprised of CQDs
(53) After the electrode grid 60 is formed, the ROIC is suitable for the deposition of a photodetector film 70, such as a CQD film as shown in
(54) With the prepared ROIC 30, which has the photodetector CQD film 70 deposited thereon, the formation into a focal plane array (“FPA”) may take place. This method will provide electrical interfacing between the ROIC and external frame-grabbing hardware and the integration of the optical pathway into a full camera system. This further processing may include steps such as deposition of anti-reflection coatings, encapsulation, mounting, or any other process that might be reasonably expected for the integration of an FPA with a camera system.
Example 2
(55) In another embodiment of this invention, the electrode grid may be deposited after the CQD film has been formed, or a second electrode grid may be deposited. In reference to example 1 above, this may be inserted as a new step in the sequence described therein, and performed after the example 1's step 1.1 and prior to example 1's step 1.2. When used as such a front-electrode, the open grid will allow more light to penetrate into the CQD film than a solid, uniform film of conducting material would allow. This is particularly important as the desired wavelength of detection increases beyond 1 micron, and the light is less able to penetrate through the conducting material. In addition, the patterned front-electrode would act to direct electrical signals to the center electrode of each pixel (electrode 32), reducing cross-talk. The CQD film must be opened to allow the subsequently deposited front-electrode to contact the common electrode contacts on the ROIC, and this opening may be accomplished through any lithograph, masking, patterning or removal process that is compatible with the ROIC and the CQD film. The use of a grid-style front electrode may help to collect more charge carriers from a thick CQD film.
Example 3
(56) In another embodiment of this invention, the ROIC would be made nearly atomically flat using chemical-mechanical planarization techniques known collectively as planarizing, prior to the deposition of the electrode grid or CQD film followed by the electrode grid. This planarization may first involve the deposition of additional insulating material, possibly chosen to act as a back electromagnetic radiation reflector to enhance the overall radiation absorption within the CQD film. Apart from the formation of a back reflector, planarization may be necessary if the height variation in the surface of the ROIC would lead to an excessively broad image plane, and loss of sharpness.
Example 4
(57) Step 1: Definition of Electrode Areas Via Photolithography
(58) 1.1 A ROIC 30 is provided as a starting workpiece, configured as shown in
(59) 1.2 Next, as shown in
(60) 1.3 Next, as shown in
(61) 1.4 Next, the ROIC 30 with conducting layer 72 and photoresist 80 can be given a thermal anneal at or near 145° C. at or near a 60 second duration, otherwise known as a ‘soft bake’. Other temperatures or durations which prepare the photoresist for light exposure will also be suitable.
(62) 1.5 As described in
(63) 1.6 After alignment on the top surface of the photoresist on ROIC 30, the photolithography mask is placed in close proximity to an ultraviolet light source.
(64) 1.7 The photoresist 80 is now prepared for removal and definition depending on the choice for photoresist. For a positive photoresist, the photoresist 80 is exposed to ultraviolet light for a duration at or near 30 seconds. Also, for a negative photoresist, UV exposure for 30 seconds will strengthen the polymers exposed, such as in the square grid areas 86, allowing the unexposed areas 88 to be safely removed in subsequent steps.
(65) 1.8 After preparation of the photoresist through exposure additional preparation steps will be undertaken specific to the photoresist chosen. The host ROIC 30, the conductive layer 72 and the photoresist 80 are given a second thermal anneal similar to step 1.4, now at a temperature at or near 100° C. and at or near 60 second duration, known as a “hard bake.”
(66) Step 2: Development of Electrode Areas Via Etching.
(67) 2.1 Next the chosen photoresist is developed. The prepared host ROIC from Step 1 is immersed completely in a suitable development solution such as RD6 for a duration at or near 60 seconds or until such time as the photoresist is fully developed. As shown in
(68) 2.2 Taking the prepared host ROIC from Step 2.1, as shown in
(69) 2.3 Two pure de-ionized water solutions are prepared, and the host ROIC is immersed within the first solution and may be lightly agitated. Then it is transferred to the second de-ionized water solution and again lightly agitated, providing a cleaning process.
(70) 2.4 After cleaning, the host ROIC is dried through flowing gaseous nitrogen of suitable purity to avoid contamination over the sample until excess liquid has been removed. Any such process to remove unwanted and excess water may be used here providing that the host ROIC is not damaged, nor the defined areas from previous steps removed.
(71) 2.5 The host ROIC is now optionally inspected for damage and proper exposure. It is at this stage combinations of any previous steps may be performed following any re-processing or chemical etching to removed unwanted areas.
(72) Step 3: Removal of Excess Photoresist
(73) The remaining photoresist 86 can be removed as shown in
(74) It is at this stage that the electrode grid 60 is finished and the ROIC is suitable for the deposition of a photodetector film 70 as shown in in
(75) With the prepared ROIC 30, which has the photodetector CQD film 70 deposited thereon, the formation into a focal plane array (“FPA”) may take place. This method will provide electrical interfacing between the ROIC and external frame-grabbing hardware and the integration of the optical pathway into a full camera system. This further processing may include steps such as deposition of anti-reflection coatings, encapsulation, mounting, or any other process that might be reasonably expected for the integration of an FPA with a camera system.
(76) The exemplary embodiment of the invention provides an electrode which:
(77) is electrically conductive, such as made from metals, or metal alloys including gold, copper, titanium, indium tin oxide or any substance, material or combination of materials which is suitably conductive for carrying electrical signals from the photodetector film;
(78) causes no underlying damage to the host ROIC to be used for extraction of electrical signals; and
(79) will not react with or interfere with the operation of the photoconductive film which will be subsequently deposited upon and near the electrode(s).
(80) can be located in close proximity on the order of the pixel pitch of the host ROIC to the electrical contacts for each pixel on the host ROIC;
(81) can be patterned into a geometry commensurate with the host ROIC including but not limited to a square grid, stripes, rings, hexagons, or other shapes provided that they are near each electrical contact on the host ROIC;
(82) can be in electrical contact with the common electrical contact provided by the host ROIC, which can provide two electrical contact terminals with which an applied electrical bias voltage may be generated;
(83) provides pixel delineation in which signals generated from electromagnetic radiation that is intercepted by a photoconductive film in proximity to pixel electrodes, is collected by that pixels electrode primarily; and allows for ready deposition and monolithic integration of a photoconductive film such as CQDs directly upon the electrode pattern which would then form a focal plane array.
(84) The exemplary methods of the invention define the electrode areas through steps of:
(85) host ROIC preparation and cleaning including but not limited to the use of solvents, plasma etches, thermal etches, or other methods to remove contaminants from host ROICs prior to further processing;
(86) definition of electrode areas involving any combination of photolithography techniques including but not limited to positive or negative photoresist, image reversal, alignment, post deposition thermal treatments, and light exposure settings which may involve the use of developing solutions;
(87) photomask development which will produce the required geometry, and be within the tolerance and support of related photolithography techniques or other object definition methods; and
(88) any number of required thermal anneals before or after any previously required step as needed to properly define electrode areas.
(89) The methods can include deposition of the conductive substance within the defined areas which conforms to the requirements through:
(90) material deposition, including electron-beam deposition, of one, two, or more layers of possible conductive substances; and
(91) removal and lift off of residual and excess photo-reactive polymers or pattern defining material or any other processing-related contaminant not needed for device operation.
(92) From the foregoing it will be observed that numerous variations and modifications may be effected without departing from the spirit and scope of the invention. It is to be understood that no limitation with respect to the specific apparatus illustrated herein is intended or should be inferred.