CN116525693A - Narrow-band EUV photoelectric detector without filter for 13.5nm - Google Patents
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Abstract
The invention relates to the technical field of narrow-band semiconductor photoelectric detection devices, in particular to a narrow-band EUV photoelectric detector which is specific to 13.5nm and does not need a filter. The structure of the detector of the invention is as follows from top to bottom: nb or Mo is used as a transparent metal conductive window layer, a p-GaN photon absorption layer, an n-SiC conductive substrate and an ohmic contact layer. The detector has an optimal operating range of 5-16nm, a narrow band response window of only 11nm, and almost no response in other bands. The device has a narrow band selective response to 13.5nm EUV light and has extremely high quantum efficiency and very low dark current levels around 13.5nm, with a dramatic improvement in performance parameters over the EUV devices currently reported. The invention provides a new thought for manufacturing the high-performance EUV detector and has good application prospect in the field of 13.5nm narrow-band photoelectric detectors.
Description
Technical Field
The invention relates to the technical field of narrow-band semiconductor photoelectric detection devices, in particular to a narrow-band EUV photoelectric detector which is specific to 13.5nm and does not need a filter.
Background
Extreme Ultraviolet (EUV) photodetectors are attracting increasing attention in several research fields, such as EUV lithography, satellite monitoring, plasma physics, and solar physics, as a key device required for many scientific and industrial applications. In particular, in lithography, a 13.5nm EUV light source successfully implements a 7nm integrated circuit fabrication process, and an EUV detector is a critical component for correcting and monitoring EUV beam-related performance parameters. Since the strong absorption of this band by most materials results in an EUV detector with very low quantum efficiency and a broad spectral response, how to obtain an EUV detector with a narrow band response performance for 13.5nm, combined with high responsivity and high quantum efficiency is a problem to be solved in market applications. At present, the performance of the mainstream Si-based EUV detector is obviously reduced after high-temperature or long-time high-energy photon irradiation, and a wide forbidden band semiconductor represented by GaN and SiC is successfully used for manufacturing a high-end short-wave photoelectric detector by using the material performance advantage, so that the Si-based EUV detector is a preferable material for preparing a new-generation ultraviolet semiconductor detector.
EUV detector structures are typically photovoltaic detectors. However, under the current technical conditions, the preparation of semiconductor photovoltaic EUV detectors faces an insurmountable bottleneck: a transparent electrode that can efficiently conduct EUV light sources is lacking. Most of the photovoltaic detectors are in a vertical structure, the photosensitive layer is located between the upper conductive layer and the lower conductive layer, when the wavelength range is expanded to the EUV range, the metal layer which is currently mainstream generates high optical absorption in the EUV range, most of incident photons are lost in the top contact layer and cannot reach the photosensitive layer to generate photocurrent, and therefore the responsivity and quantum efficiency are extremely low. Solutions have been proposed in previous studies to further reduce metal thickness or use patterned metal films, but are difficult to realize industrially; graphene has higher EUV light transmittance, and is considered as a top electrode material of an EUV detector by research, but the graphene electrode photoelectric detector generally has the problems of large leakage current, poor uniformity and the like, so that the practical application prospect is limited. Therefore, how to effectively improve the detection efficiency and the device stability of the extreme ultraviolet detector is one of the key scientific problems faced by the design and the preparation of the extreme ultraviolet detector.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a narrow-band EUV photoelectric detector without a filter for 13.5nm, which uses Nb or Mo as a detector of a transparent metal conductive window layer, and can effectively improve the responsivity and quantum efficiency of the EUV detector.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the invention provides a narrow-band EUV photoelectric detector without a filter for 13.5nm, which comprises the following structures from top to bottom: the p-GaN photon absorption layer, the n-SiC conductive substrate and the ohmic contact layer are made of Nb or Mo as transparent metal.
As shown in fig. 1a, gaN has a stronger absorption of 13.5nm light than Si or SiC, which means that if GaN is used as the light absorbing layer instead of Si and SiC, which are currently mainstream, it would theoretically have a higher detection efficiency.
The metals Nb and Mo have natural selective transmission for EUV light, and the theoretical transmission of these two metals with Au (the top metal layer used in current EUV detector processes) in the EUV band is shown in fig. 1b, where Nb can reach more than 80% transmission at 13.5nm, mo also has near 80% transmission at 13.5nm, and almost 0 transmission after 20-25 nm. Therefore, nb and Mo can be used as ideal materials for the top electrode of the EUV detector, and the detector can have selective response while ensuring the detection efficiency.
Preferably, the ohmic contact layer is a Ti metal layer, and the structure of the detector comprises a P-N structure facing away from Mo/P-GaN/N-SiC/Ti and a P-N structure facing away from Nb/P-GaN/N-SiC/Ti.
Preferably, the thickness of the transparent metal conductive window layer is 30-70 nm, the thickness of the p-GaN photon absorption layer is 50-150 nm, the thickness of the n-SiC conductive substrate is 6-10 μm, and the thickness of the ohmic contact layer is 30-70 nm.
Preferably, the carrier concentration of the p-GaN photon absorption layer is 10 15 ～10 17 cm -3 The carrier concentration of the n-SiC conductive substrate is 10 14 ～10 16 cm -3 。
The invention also provides a preparation method of the narrow-band EUV photoelectric detector without a filter for 13.5nm, which comprises the following preparation processes:
s1, growing a p-GaN photon absorption layer on an n-SiC conductive substrate;
s2, evaporating a Ti metal electrode on the surface of the n-SiC substrate;
s3, carrying out photoetching on the p-GaN photon absorption layer, and evaporating an Nb metal electrode or a Mo metal electrode on the surface of the p-GaN;
and S4, rapidly annealing the metal electrode after the electrode evaporation is finished.
Preferably, the annealing is at N 2 Annealing at 550 ℃ for 2min in the atmosphere.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses Nb or Mo as the detector of the transparent metal conductive window layer, and the effect of wavelength selective response can be achieved by using both the Nb layer and the Mo layer. The detector has a p-GaN/n-SiC structure, the wave band of 5-16nm is the optimal range of the detector, the narrow-band response window of only 11nm is provided, the other wave bands have almost no response, the narrow-band detector is excellent, and R 13.5nm /R 35.5 nm The response inhibition ratio is as high as 10 3 High sensitivity selective responsiveness is achieved. Meanwhile, the detector keeps high responsivity and high quantum efficiency in a 13.5nm wave band, the responsivity and the quantum efficiency of a Mo layer and a Nb layer under 0V bias are respectively 0.116A/W, 1046.03 percent and 0.132A/W and 1214.79 percent, and compared with the traditional EUV device taking Au as a metal top layer, the performance parameters of the detector are greatly improved. The invention provides a new idea for manufacturing the high-performance EUV detector, and the 13.5nm narrow-band photoelectric detectorThe field has good application prospect.
Drawings
FIG. 1 shows the absorbance contrast (a) of GaN with Si, siC in the EUV band; transmittance of Mo, nb and Au in EUV band contrast (b);
FIG. 2 is a schematic diagram of the structure of a sample A device;
FIG. 3 is a schematic diagram of the structure of a sample B device;
in fig. 2 and 3, 1, p-GaN photon absorption layers; 2. an n-SiC conductive substrate; 3. a Ti metal layer (electrode); 4. mo metal layer (electrode); 5. nb metal layer (electrode);
FIG. 4 is the results of the I-V test of sample A, B, C under 13.5nm irradiation and darkness;
FIG. 5 is a plot of responsivity of sample A, B, C as a function of wavelength for zero bias, wherein (a) sample A and sample B, (B) sample C;
FIG. 6 is a graph of EQE versus wavelength for sample A, B, C;
FIG. 7 is a response cycle for samples A and B;
FIG. 8 shows the response speed (a) of sample A; response speed (B) of sample B.
Detailed Description
The following describes the invention in more detail. The description of these embodiments is provided to assist understanding of the present invention, but is not intended to limit the present invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The experimental methods in the following examples, unless otherwise specified, were conventional, and the experimental materials used in the following examples, unless otherwise specified, were commercially available from conventional sources.
Example 1 narrow-band EUV detector facing away from Mo/p-GaN/n-SiC/Ti Structure
1. The device structure is as follows: the structure of the narrow-band EUV detection device of the present embodiment is as shown in fig. 2, and from top to bottom, in order: 4. mo metal layer (electrode); 1. a p-GaN photon absorption layer; 2. an n-SiC conductive substrate; 3. the Ti metal layer (electrode) is a P-N structure facing away from the Mo/P-GaN/N-SiC/Ti structure.
2. Specific parameters of the device structure: the Mo contact electrode is used as an anode conductive window to cover the photon absorption layer for collecting photo-generated carriers, and the thickness of the Mo contact electrode is 50nm; p-GaN as photon absorption layer with thickness of 100nm and carrier concentration of 10- 17 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the n-SiC is an electron collecting layer with the thickness of 8 mu m and the carrier concentration of 10 percent 16 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the The ohmic contact Ti layer was used to collect electrons and had a thickness of 50nm.
3. Preparing a device:
s1, firstly, carrying out hydrogen heat treatment on an n-SiC conductive substrate, wherein the carrier concentration is 10 16 cm -3 Epitaxially growing a p-GaN photon absorption layer with the thickness of 100nm on an N-type silicon carbide substrate with the thickness of 8 mu m by adopting a Metal Organic Chemical Vapor Deposition (MOCVD) method, wherein the carrier concentration is 10 17 cm -3 ；
S2, after the growth is finished, cleaning the surface of the sample by adopting a method of sequentially ultrasonically cleaning toluene, acetone, ethanol and deionized water for 5 min; then, adopting vacuum coating equipment to vapor-deposit a Ti metal electrode with the thickness of 50nm on the lower surface of the n-SiC substrate, and annealing for 2min at 550 ℃ in a nitrogen atmosphere after the vapor deposition of the electrode is finished;
s3, spin coating photoresist on the surface of the p-GaN film, pre-baking, performing ultraviolet exposure on the photoetching sample area, removing the photoresist on the exposure area by using NaOH solution, etching the photoetching sample by using an ICP etching system, and vacuumizing after etching is finished;
s4, a Mo metal layer with the thickness of 50nm is evaporated on the surface of the p-GaN film, and after the electrode evaporation is finished, the film is annealed at 550 ℃ for 2min in a nitrogen atmosphere, so that a narrow-band EUV detector with a structure facing away from the Mo/p-GaN/n-SiC/Ti is prepared and is marked as a sample A.
Example 2 narrow-band EUV detector facing away from Nb/p-GaN/n-SiC/Ti Structure
1. The device structure is as follows: the structure of the narrow-band EUV detection device of the present embodiment is as shown in fig. 3, and from top to bottom: 5. nb metal layer (electrode); 1. a p-GaN photon absorption layer; 2. an n-SiC conductive substrate; 3. the Ti metal layer (electrode) is a P-N structure facing away from the Nb/P-GaN/N-SiC/Ti structure.
2. Specific parameters of the device structure: the Nb contact electrode is used as an anode conductive window to cover the photon absorption layer for collecting photo-generated carriers, and the thickness of the Nb contact electrode is 50nm; p-GaN as photon absorption layer with thickness of 100nm and carrier concentration of 10- 17 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the n-SiC is an electron collecting layer with the thickness of 8 mu m and the carrier concentration of 10 percent 16 cm -3 The method comprises the steps of carrying out a first treatment on the surface of the The ohmic contact Ti layer was used to collect electrons and had a thickness of 50nm.
3. The device fabrication procedure was the same as in example 1, except that a 50nm thick Nb metal layer was evaporated on the p-GaN thin film surface in step S4, to produce a narrow-band EUV detector facing away from the Nb/p-GaN/n-SiC/Ti structure. And is designated as sample B.
Comparative example 1 narrow-band EUV detector facing away from Au/p-GaN/n-SiC/Ti structure
The control group made the conductive window layer as Au metal layer used in the current mainstream EUV detector, the electrode thickness was still 50nm, the electrode size, the main structure and the process flow were all the same as samples a and B, and the detector was made and designated as sample C.
Experimental example 1 characterization of the performance of a narrow-band EUV detector
1. I-V test of sample A, B, C under 13.5nm irradiation and darkness
Dark current level is an important performance indicator of EUV photodetectors, reflecting the degree of crystal defects and the quality of the device structure. Sample A, B, C was subjected to I-V test under 13.5nm irradiation and darkness, respectively, and the test results are shown in FIG. 4. All three samples exhibited very low dark current (about 8.13 pA) at a bias voltage range of 0V, with a significant increase in the reverse polarization current of sample a (about 61.37 μa) under EUV illumination at 13.5nm, and of sample B about 70.12 μa, such a high light-to-dark current ratio indicating a high on-off ratio of the detector; while the photocurrent of sample C was only 4.92nA, which demonstrates that Mo and Nb layers both contribute significantly to reducing photon absorption in the EUV band as the detector top metal layer. At the same time, the response curve of the detector A, B remains nearly constant over the reverse bias voltage range of 0-10V, which also demonstrates the stability of the device in operation.
2. Photoresponsivity characterization
Photo responsivity R λ Is one of the most important parameters of the photodetector, which reveals the gain of the input and output of the photodetector system, and can be expressed by the formula R λ =Δi/(PS), where Δi is the difference between the dark and bright currents, P is the incident optical power density, and S is the effective area of the device operation. By testing the spectral response curve of the detector in the wavelength range of 2-40 nm in the EUV spectral region, it was found that detectors A and B had significant photocurrent gain when the incident light wavelength was in the range of 4-17 nm, as shown in FIG. 5, the responsivity of sample A was about 116mA/W at 13.5nm and about 53.2 μA/W at 35.5nm, so that the suppression ratio of sample A was about 2.18X10 3 The method comprises the steps of carrying out a first treatment on the surface of the The response of sample B was about 132mA/W at 13.5nm and about 50.7. Mu.A/W at 35.5nm, so that the inhibition ratio of sample B was about 2.60X 10 3 The method comprises the steps of carrying out a first treatment on the surface of the Sample C had responsivity of about 0.927mA/W and 0.145mA/W, respectively, at 13.5nm and 35.5nm, and an inhibition ratio of about 6.4.
From the above analysis, it was demonstrated that samples A and B had higher response characteristics for a band around 13.5nm with a 13.5nm/35.5nm responsivity suppression ratio of up to 10 3 The method comprises the steps of carrying out a first treatment on the surface of the In addition, the detector obtained by the sample B has a narrow-band response window of 11nm, the wave band of 5-16nm is the optimal range of the detector, and the other wave bands have almost no response; sample a also had a response half-width of only 13nm. Whereas sample C has almost no selective response properties at all in the 13.5nm band. Therefore, it is demonstrated that samples A and B according to the invention are more suitable for EUV detection in the 13.5nm band, with significantly better selective response properties.
3. Quantum efficiency characterization
The quantum efficiency is used to define the percentage of photons received by a photodetector or other device from its light-receiving surface to electron-hole pairs, i.e., the quantum efficiency is equal to the number of photon-generated electrons divided by the number of incident photonsWherein->Is Planck constant, c is light velocity, e is electron charge, lambda is wavelength of incident light, R λ Representing the reflectivity of the photodetector surface. As shown in FIG. 6, the curves of the quantum efficiency (EQE) of samples A, B and C along with the change of wavelength are shown that the quantum efficiency of A reaches 1063.36% at 13.5nm, the quantum efficiency of sample B is about 1214.79%, the quantum efficiency of a novel SiC wide-bandgap semiconductor EUV photovoltaic detector reported at 13.5nm is 960% (4H-SiC delta n-i-p extreme ultraviolet detector with gradient doping-induced surface junction), and the two detectors are higher than the values; and sample C does not have significant EUV band-selective responsiveness compared to samples a and B, the EQE at 13.5nm is only 8.51%.
4. Switch photoresponse characterization
In the field of EUV detector operation, devices have high demands on ultra-fast time response speeds. The invention uses 13.5nm pulsed light to simulate ultra-fast changing EUV signal sources and test samples A and B for time response. Fig. 7 shows first the time-varying photovoltaic response of the device under EUV signals, which is relatively stable over several periods. To analyze the speed of the time response more clearly, the single response period is amplified, and the test results for sample a and sample B are shown in fig. 8a and B, respectively, with the response rise time (τ r ) Defined as the time for the current to increase from 10% to 90% of the peak value at turn-on, decay time (τ d ) Defined as the time that the current drops from 90% to 10% of the peak value when off. For sample A, extracted τ r And τ d Values are 28.6ns and 312.7ns, respectively, τ for sample B r And τ d The values are 24.2ns and 386.5ns respectively, which indicates that the device has a response speed of ultra-high speed. This speed is mainly due to the high lattice quality of GaN and the strong built-in electric field effect of the detector structure designed by the invention, i.e. the response to rapid separation of photo-generated carriers is enhanced, thus being sufficient to meet the requirements for detecting rapidly changing EUV signals.
In summary, in order to enhance the performance of the EUV detector in the application field, the vertical photovoltaic detector using Mo and Nb as transparent conductive windows is fabricated, and has excellent light responsivity and quantum efficiency. The device has narrow-band selective response to 13.5nm EUV light, extremely high quantum efficiency and extremely low dark current level near 13.5nm, and extremely high response speed, and lays a foundation for the device in the EUV industrial application field.
The embodiments of the present invention have been described in detail above, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, and yet fall within the scope of the invention.
Claims (6)
1. The narrow-band EUV photoelectric detector without a filter for 13.5nm is characterized in that the structure of the detector is as follows from top to bottom: the p-GaN photon absorption layer, the n-SiC conductive substrate and the ohmic contact layer are made of Nb or Mo as transparent metal.
2. Narrow-band EUV photodetector for 13.5nm without filter according to claim 1, characterized in that the ohmic contact layer is a Ti metal layer, the structure of the detector comprises a P-N structure facing away from Mo/P-GaN/N-SiC/Ti and a P-N structure facing away from Nb/P-GaN/N-SiC/Ti.
3. A narrow band EUV photodetector for 13.5nm without a filter according to claim 1, wherein the transparent metal conductive window layer has a thickness of 30 to 70nm, the p-GaN photon absorption layer has a thickness of 50 to 150nm, the n-SiC conductive substrate has a thickness of 6 to 10 μm, and the ohmic contact layer has a thickness of 30 to 70nm.
4. Narrow-band EUV photodetector for 13.5nm without filter according to claim 1, characterized in that the carrier concentration of the p-GaN photon absorption layer is 10 15 ～10 17 cm -3 The carrier concentration of the n-SiC conductive substrate is 10 14 ～10 16 cm -3 。
5. A method of manufacturing a narrow-band EUV photodetector for 13.5nm without a filter according to any of claims 1 to 4, characterized in that the manufacturing procedure comprises:
s1, growing a p-GaN photon absorption layer on an n-SiC conductive substrate;
s2, evaporating a Ti metal electrode on the surface of the n-SiC substrate;
s3, carrying out photoetching on the p-GaN photon absorption layer, and evaporating an Nb metal electrode or a Mo metal electrode on the surface of the p-GaN;
s4, after the electrode evaporation is finished, the metal electrode is annealed rapidly.
6. The method of claim 5, wherein the annealing is performed at N 2 Annealing at 550 ℃ for 2min in the atmosphere.
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