TWI733183B - Fluorescent nitrogen-vacancy diamond (fnvd) sensing sheet, manufacturing method and uses thereof, sensor, and lithography apparatus - Google Patents

Abstract

The present disclosure provides a Fluorescent Nitrogen-Vacancy Diamond (FNVD) having a plurality of nitrogen-vacancy centers with a concentration about 1 ppm to 10000ppm.

Description

Fluorescent nitrogen vacancy diamond sensor sheet, manufacturing method and use method thereof, sensor, and lithography equipment

The present invention generally relates to a light sensing element, its manufacturing method, and its use method; specifically, the present invention relates to an FNVD sensing sheet, its manufacturing method and its use method, sensors, and lithography equipment.

The wavelength range of vacuum-ultraviolet radiation (VUV) is between about 30 to about 200 nm, which is equivalent to an energy of 6.2 eV to 41.3 eV; extreme ultraviolet radiation (EUV) probes the wavelength down to About 10 nm; In addition to these wavelength ranges, there are high-energy X-rays with wavelengths shorter than 12 nm. The most sensitive sensor on the market that detects these wavelength ranges is photomultiplier (PMT). However, the photomultiplier tube limits the detection range due to the use of the light window. For example, a solar blind PMT (solar blind PMT), because the MgF ₂ light window is used, the shortest wavelength of VUV that can be directly detected is only about 115 nm, while VUV/EUV/X-rays with a wavelength shorter than 115 nm cannot Detect with a positive-blind photomultiplier tube.

To overcome the limitation of the light window, fluorescent materials can be used as VUV/EUV/X-ray sensors. The principle of operation is to excite the fluorescent substance with VUV/EUV/X-rays to make it emit fluorescence, and then measure the fluorescence with a photomultiplier tube or equivalent detector to sense VUV/EUV/X-rays. Traditionally, the fluorescent substances used as VUV/EUV/X-ray sensors are mostly organic substances. For example, the most widely used fluorescent substance is sodium salicylate. The energy of VUV/EUV/X-rays is high enough to break any chemical bonds. Therefore, the biggest problem in using such organic fluorescent materials as VUV/EUV/X-ray sensing applications is the rapid aging of fluorescent materials.

The present invention uses diamond with a vacant center as the VUV/EUV/X-ray sensing material, which can not only extend the sensing spectral range of the traditional photomultiplier tube to the VUV/EUV/X-ray section, but also solve the problem of traditional organic fluorescent materials. The problem of rapid aging.

In order to solve the problems in the prior art, the inventor of this case proposed a proper inventive concept, which is embodied by the following many different embodiments.

One embodiment of the present invention is a Fluorescent Nitrogen-Vacancy Diamond (FNVD) sensor chip, which has a complex nitrogen vacancy center with a concentration of about 1-10000 ppm.

In one embodiment, when the first radiation is absorbed, the FNVD sensor sheet emits second radiation; the first radiation has a wavelength range shorter than 250nm; the second radiation has a wavelength range between 540-850nm .

In one embodiment, the spectrum of the second radiation has a peak wavelength at about 573-578 nm nm.

In one embodiment, the FNVD sensor chip converts the first radiation into a fluorescent light with a quantum conversion efficiency of about 0.1 to about 17.

Another embodiment of the present invention is a manufacturing method of the FNVD sensing sheet according to claim 1, which includes preparing FNVD powder; and molding the FNVD powder.

In one embodiment, preparing the FNVD powder further includes generating vacancy defects in the type Ib diamond powder, and diffusing the vacancy defects around the nitrogen atoms in the FNVD powder.

In one embodiment, it further includes annealing the FNVD powder at a temperature of about 600°C to 1000°C.

In one embodiment, it further includes a filler mixed in FNVD powder to be composed of at least one element or its compound from the following group: molybdenum (Mo), tungsten (W), niobium (Nb), tantalum (Ta ), rhenium (Re), titanium (Ti), vanadium (V), iron (Fe), cobalt (Co), nickel (Ni), aluminum (Al), zirconium (Zr), magnesium (Mg), calcium (Ca) ), cesium (Cs), silicon (Si), boron (B).

In one embodiment, it further comprises molding the FNVD powder by pressing, spraying, or heating.

In one embodiment, it further comprises heating the FNVD powder to a temperature between 200°C and 1500°C in an oxygen-deficient environment or in a vacuum.

In one embodiment, it further includes removing graphitic carbon from the surface of the FNVD powder.

Another embodiment of the present invention is a sensor including a first sensor having a complex nitrogen vacancy center diamond with a concentration of about 1-10000 ppm, configured to absorb first radiation and emit second radiation; and The detector is configured to detect the second radiation.

In one embodiment, the first radiation has a wavelength range shorter than 250 nm; and the second radiation has a wavelength range between 540-850 nm.

In one embodiment, the second sensor includes a photomultiplier tube, a photocell, a photodiode, or a solar cell.

In one embodiment, when the first radiation is absorbed by the first sensor, the first sensor converts the first radiation into a fluorescent light with a quantum conversion efficiency of at least 0.1.

Another embodiment of the present invention is a lithography device including the aforementioned sensor.

In one embodiment, it further includes a radiation source configured to emit the first radiation.

In one embodiment, it further includes a processor configured to generate the emission spectrum of the second radiation.

Another embodiment of the present invention is a method for sensing radiation, including providing a FNVD sensor sheet as claimed in claim 1, which has a complex nitrogen vacancy center diamond with a concentration of about 1-10000 ppm; exposing the FNVD sensor sheet To the first radiation, the FNVD sensing sheet emits second radiation corresponding to the first radiation after being exposed to the first radiation; and generates a spectrum of the second radiation.

In one embodiment, the first radiation has a wavelength range shorter than 250 nm; and the second radiation has a wavelength range between 540-850 nm.

Refer to Figure 1, which is a schematic diagram of the structure of a Fluorescent Nitrogen-Vacancy Diamond (FNVD). Nitrogen-vacancy center (NV center) is a kind of point defects of diamond, which consists of a nitrogen atom and a vacancy defect adjacent to the nearest lattice point of the diamond. , And diamonds that include such point defects are called nitrogen-vacant diamonds. In this disclosure, nitrogen-vacant diamonds are used to emit fluorescence to detect radiation, so they are also called fluorescent nitrogen-vacant diamonds. In addition to the vacancy center formed by a nitrogen atom and a lattice vacancy, in another embodiment, the vacancy center of a diamond can also be formed by the combination of two nitrogen atoms and a lattice vacancy, which can be also called H3 vacancy center (H3 center), this is still a nitrogen-containing defect structure. The present invention is described below using a vacancy center formed by a nitrogen atom and a lattice vacancy as an example.

Figure 2 shows the photoluminescence (PL) spectrum of FNVD irradiated with 250nm-525nm radiation at a temperature of about 300K. The nitrogen vacancy center of FNVD powder includes two valence states ^{: neutral ((NV) 0} ) and negative ((NV) ^{− ).} From the PL spectrum in Figure 2, two zero-phonon lines at 575.0nm and 638.0nm can be observed. The zero-phonon line at 575.0nm is derived from the electron transfer at the neutral valence nitrogen vacancy center. The 638.0nm zero phonon line is derived from the electron transfer ( ³ A→ ³ E) from the center of the nitrogen vacancy in the negative valence state.

Figure 3, Figure 4, and Figure 5 show the PL spectra of FNVD irradiated with VUV/EUV/X-rays with wavelengths of 1.03nm-200nm (1200-6.20 eV) at a temperature of about 300K, and the coordinate axis scales are organized by the indicated multiples. The particle diameter of FNVD is about 100 nm, which is greater than the depth (<30nm) of the particles through which VUV/EUV/X-ray light passes through FNVD. Compared with Figure 2, the contours of the spectral lines in Figure 3 are similar, with a 576 nm zero phonon line accompanied by a phonon sideband with a peak of about 620 nm, all of which are at the center of the neutral valence nitrogen vacancy center. feature. However, the feature of the vacancy center of negatively charged nitrogen nitrogen was not found: the zero phonon line of 638.0 nm. This phenomenon can be explained as the electron hole recombines due to relaxation, and the released energy is about 5.49eV (equivalent to a wavelength of 226nm), which is enough to ionize the vacancy center of the negative valence state, and then form a neutral center excited by the electron. , Because this process only requires 4.8eV (250nm) of energy. This result shows that the photoionization of FNVD is a fairly high-efficiency process, which is similar to irradiating FNVD with electron radiation during cathodoluminescence measurement.

Figure 4 shows the PL spectrum of FNVD irradiated with EUV with energy 50-206.6 eV (equivalent to wavelength 6nm-24.8nm) at a temperature of about 300K. Figure 5 shows the PL spectrum of FNVD irradiated by X-rays with energy of 283.07-1200 eV (equivalent to wavelength 1.03nm-4.38nm) at a temperature of about 300K. Both Fig. 4 and Fig. 5 have the same or similar spectral characteristics as Fig. 3. In addition, if the used VUV/EUV/X-ray energy is further increased or set to be greater than about 4.8 eV, that is, light waves with a wavelength shorter than about 250 nm can also obtain similar spectral line profiles.

Referring to FIG. 6, FIG. 6 shows the quantum conversion efficiency of the excitation energy to 1450 eV when the FNVD emits a fluorescence wavelength of 620 nm at a temperature of about 300 K. The FNVD was irradiated with excitation light of 0.86nm-300nm at a temperature of about 300K, and the excitation spectrum of the FNVD at 620nm fluorescence was measured. Standardizing the PL excitation spectrum can obtain the quantum conversion efficiency as shown in FIG. 6. Those skilled in the art should know that the quantum conversion efficiency here refers to the ratio of the number of excited electrons returning to the ground state by emitting fluorescence to the number of excited photons.

In one embodiment, the PL excitation spectrum starts at about 5.49 eV (226 nm), and the quantum conversion efficiency peaks at about 7.0 eV (177 nm). Obviously, the starting position of 226nm coincides with the absorption edge of pure diamond, which means that the PL signal is directly related to the interband absorption of diamond. After the absorption margin, for the emission fluorescence wavelength of 620nm, the lowest quantum yield is about 0.19 at 12.0 eV (100 nm), and after this value, as the excitation energy increases, the quantum yield It also increases, as shown in Figure 6, for example, reaching a peak of 17 at 750eV (1.65nm). Such a large quantum yield (＞＞1) means that multiple electron hole pairs can be generated when excited in a high energy range such as VUV/EUV/X-ray. This result is similar to the photocurrent measurement of the diamond substrate with a photodetector. The result is consistent.

It is worth noting that the PL excitation spectrum of FNVD is continuous in the VUV/EUV/X-ray band disclosed in the present invention. In addition, the larger quantum yield also means that FNVD is very suitable as an effective VUV/EUV/X-ray sensor.

Referring to FIG. 7, FIG. 7 shows the relationship between the intensity of the 620 nm radiation generated by the FNVD and the width of the incident light slit under the irradiation of various wavelengths of radiation in an environment with a temperature of about 300K. For the synchrotron light source (synchrotron light source) deflection magnet (bending magnet) beam, when the entrance slit (entrance slit) is fully opened, the correlation between photon flux and exit slit (exit slit) is linear . It can be seen from FIG. 7 that under different wavelengths, the intensity of PL emitted light has a linear relationship with the width of the exit light slit. This result shows that the PL emission intensity of FNVD and the photon flux are linearly dependent, demonstrating the applicability of using FNVD as a VUV sensor.

The detailed data of Figure 7 is recorded as follows: (a) 30nm; (b) 60nm (ordinate scale (ordinate scale) magnified 3 times); (c) 90nm (coordinate axis scale magnified 6 times); (d) 110nm (coordinate axis) The scale is enlarged by 5 times); (e) 140nm (the scale of the coordinate axis is enlarged by 2.5 times); (f) 170nm; and (g) 200nm (the scale of the coordinate axis is reduced by 1 times).

To test the actual operability of the FNVD sensor, the FNVD powder can be pasted on a quartz viewport with polyethylene tape. Refer to Figure 8. Figure 8 shows (a) the light window (viewport), (b) the polyethylene tape on the light window, and (c) the transmission spectrum of the FNVD powder pasted on the light window through the polyethylene tape ( transmission spectrum). The penetration rate of the FNVD sensor (curve (c)) is about 4% at about 300nm, and monotonically increasing, increasing to about 10% at about 600nm, and about 15% at about 900nm The penetration rate of 4% to 15% is sufficient for measurement.

Referring to FIG. 9, the absorption spectrum of gaseous molecules can also be measured using the aforementioned FNVD sensor. A sample cell for the sample to be tested is set between the VUV light source and the FNVD sensor. When the VUV passes through the sample tube, part of the wavelength range will be absorbed by the sample to be tested. The VUV passing through the sample tube is then irradiated on the FNVD sensor, and a photomultiplier (PMT) is used to detect the FNVD sensor. The fluorescent signal emitted. By this method, the absorption cross section of a gaseous molecule in the sample tube can be known. In one embodiment, (a) a FNVD sensor and (b) a sodium salicylate (sodium salicylate) sensor are used to measure gaseous oxygen molecules in the wavelength range of 115-200 nm at a temperature of about 300K in the above-mentioned manner. The measurement results of the absorption cross section are shown in Figure 9.

Considering the possible systematic errors of the FNVD sensor, the experimental uncertainty of the absorption cross section is within 15%. The absorption of oxygen molecules in the wavelength range of 130-175nm is the Schumann-Runge continuum (Schumann–Runge continuum). In the Schumann Lungi continuous belt, the comparison value of (a) the FNVD sensor and (b) the sodium salicylate sensor meets the experimental uncertainty. For example, (a) the absorption cross-section measured by the FNVD sensor at 143nm is 15.8Mb, which is similar to (b) the absorption cross-section measured by the sodium salicylate sensor at 143nm of 15.1 Mb. Also for example, (a) FNVD absorption cross section of the sensor at 124.4 nm was measured 56.7 Mb (energy state ^{(state) E 3 Σu -)} , similar to (b) in the absorption of sodium salicylate sensor measurement 124.4nm The cross-section is 57.6 Mb. (A) The absorption cross section measured by the FNVD sensor at 120.5 nm is 18.9 Mb (energy state ¹ Δ _g ). Approximate to (b) the absorption cross section of the sodium salicylate sensor measured at 120.5 nm, 18.4 Mb. The difference measured by (a) the FNVD sensor and (b) the sodium salicylate sensor in Figure 9 is within 5%. This result shows that the FNVD sensor and the conventional sodium salicylate sensor are in The measurement of the absorption cross section of gaseous molecules has the same effect in application.

Referring to Figure 10, Figure 10 is a time decay curve of the fluorescence intensity of the (a) FNVD sensor and (b) the sodium salicylate sensor irradiated with radiation with a wavelength of 60 nm. As shown in Fig. 10, after the FNVD sensor is continuously irradiated with radiation with a wavelength of 60nm at a temperature of about 300K for one hour, the intensity of the fluorescence decays less than 2%. The sodium salicylate sensor decays by about 42% under the same operating conditions. In addition, the fluctuating fluorescence of the FNVD sensor is within 0.6%, which is close to the stability of the synchrotron radiation source. However, the emission fluorescence of the sodium salicylate sensor fluctuates by about 5%. The above results can prove that the stability of the FNVD sensor is better than that of the sodium salicylate sensor.

Considering the repeatability performance of the FNVD sensor detection, Figure 11 shows the relationship between the switch sensor and the emission fluorescence intensity when the FNVD sensor is irradiated with radiation with a wavelength of 60nm at a temperature of about 300K. It can be seen from Fig. 11 that the fluorescence intensity of the FNVD sensor can be recovered almost completely in each switching cycle. This result can prove that the FNVD sensor has satisfactory reproducibility.

Referring to FIG. 12, FIG. 12 is a step 100 of the manufacturing process of an FNVD sensor chip according to an embodiment of the present invention. Step 100 of the manufacturing process includes preparing FNVD powder (Step 102); mixing with other fillers (Step 104); and pressing, spraying, or thermoforming (Step 106). The following will describe each step separately.

Referring to FIG. 13, FIG. 13 is a manufacturing process of FNVD powder according to an embodiment of the present invention. FNVD powder can be prepared from type-Ib diamond powder. Those with ordinary knowledge in the technical field should know that type Ib diamond powder has a trace amount of nitrogen (for example, 0.05% or 500 ppm), which exists in the form of isolated nitrogen atoms. In some embodiments, the type Ib diamond powder has a nanometer-scale diameter, for example, a diameter of about 1 nm, 10 nm, or 100 nm.

In some embodiments, type Ib diamond powder may be pre-treated. For example, use concentrated mixed acid for purification. In some embodiments, deionized water may be used to wet the powder between the steps of making the FNVD powder.

In some embodiments, the manufacturing method of FNVD powder may include irradiating the Ib type diamond powder with an ion beam to break the bonds of carbon atoms, thereby generating vacancy defects. In some embodiments, electron beam or proton beam irradiation may be used. In some embodiments, the flux of the beam used can be adjusted to produce an appropriate number of lattice vacancies. In some embodiments, an electron beam with a flux of about 10 ¹⁹ /cm ^{2 may be used.} In some embodiments, a Rhodotron E-beam Accelerator, a synchrotron radiation source, an ion implanter, or other instruments that can generate the aforementioned energy may be used.

In some embodiments, the manufacturing method of the FNVD powder may further include annealing the powder at a high temperature to diffuse the lattice vacancies around the nitrogen atoms in the powder to generate nitrogen vacancy centers (NV) ⁻ . In some embodiments, the annealing temperature and time can be controlled to adjust the concentration of nitrogen vacancy centers. In some embodiments, the annealing temperature may be between about 600°C and 1000°C. In some embodiments, the powder may be annealed at 800°C for 2 hours. In some embodiments, annealing can be performed in an oxygen-deficient environment. In some embodiments, annealing may be performed in a vacuum environment.

In some embodiments, the manufacturing method of FNVD powder may further include removing graphitic carbon on the surface. In some embodiments, graphitic carbon can be removed by using a concentrated mixed acid cleaning powder, such as a mixed solution of sulfuric acid and nitric acid. In some embodiments, graphitic carbon can be removed by heating the powder. In some embodiments, the powder is oxidized in air at 450° C. for 1 hour to remove graphitic carbon.

In some embodiments, the manufacturing method of FNVD powder may further include analyzing the concentration of nitrogen vacancy centers. In some embodiments, Fourier-transform infrared spectroscopy (FTIR) and/or ultraviolet-visible spectroscopy (UV-VIS) can be used to utilize the optical properties of FNVD powder Calculate the concentration of the nitrogen vacancy center. For example, in some embodiments, FTIR can be used to measure the absorption coefficient of the FNVD powder for a certain radiation intensity, and then the concentration of the nitrogen vacancy center in the FNVD powder can be analyzed. In some embodiments, UV-VIS spectroscopy can be used to analyze the absorption intensity of the zero phonon line, and then analyze the concentration of the nitrogen vacancy center.

In some embodiments, the concentration of nitrogen vacancy centers in the prepared FNVD powder is greater than 1 ppm and less than 5 ppm. In some embodiments, the concentration of nitrogen vacancy centers in the prepared FNVD powder is about 1 ppm to 1000 ppm. In some embodiments, the concentration of nitrogen vacancy centers in the prepared FNVD powder is not less than 1000 ppm. In some embodiments, the concentration of nitrogen vacancy centers in the prepared FNVD powder is about 1000-10000 ppm. In some embodiments, the concentration of nitrogen vacancy centers in the prepared FNVD powder is about 1-10000 ppm.

Referring back to FIG. 12, in some embodiments, the manufacturing process 100 in which FNVD powder is manufactured as a sensor chip type further includes mixing the manufactured FNVD powder with other additives (step 104). In some embodiments, the filler may include refractory metals, such as molybdenum (Mo), tungsten (W), niobium (Nb), tantalum (Ta), rhenium (Re), and alloys thereof. In some embodiments, the filler may include transition metals, such as titanium (Ti), vanadium (V), iron (Fe), cobalt (Co), nickel (Ni), and the like. In some embodiments, the filler may include non-metallic materials, such as silicon (Si), boron (B), and compounds thereof. In some embodiments, the filler may include metal oxides such as aluminum oxide, zirconium oxide, magnesium oxide, calcium oxide, and cesium oxide. In some embodiments, the filler may include calcium bromide, Boehmite (AlO(OH))). In some embodiments, the filler may include a polymer, such as polyethylene, polypropylene, and the like. In some embodiments, the filler to be added can be appropriately selected according to different molding methods. In some embodiments, mixing other fillers in the FNVD powder can further change the properties of the FNVD powder. In some embodiments, the filler added to the FNVD powder does not substantially change the optical properties of the FNVD powder.

Continuing to refer to FIG. 12, in some embodiments, the manufacturing process 100 for manufacturing the FNVD powder as a sensor chip type further includes molding the manufactured FNVD powder by pressing, spraying, or heating (step 106 ). The pressing, spraying, or heating forming methods may include conventional ceramic forming methods, glass forming methods, or diamond forming methods. However, the present invention is not limited to the above exemplary molding method. For example, the FNVD sensor sheet can also be molded by 3-Dimentional Printing. In some embodiments, step 106 further includes sintering the FNVD powder at high temperature. In some embodiments, step 106 further includes heating the FNVD powder to a temperature between 200°C and 1500°C in an oxygen-deficient environment or in a vacuum.

Referring to FIG. 14, FIG. 14 shows a sensor 200 according to an embodiment of the present invention. The sensor is a sensing system or device composed of several sensors. In some embodiments, the sensor 200 includes a first sensor 202 and a second sensor 204.

In some embodiments, the first sensor 202 is, for example, the FNVD sensor sheet described above with reference to FIGS. 12 and 13, which has a plurality of nitrogen vacancy centers. In some embodiments, the first sensor 202 is coated on a light window or located on the wall of a photomultiplier tube, with the FNVD powder described above, for example, with reference to FIG. 13 and located at the light receiving place above it. In some embodiments, the FNVD powder is coated to form an FNVD coating on the light window or the wall of the photomultiplier tube. In some embodiments, the FNVD powder is adhered to the light window or the wall of the photomultiplier tube through tape or other tools. In other embodiments, FNVD powder is sintered with silicon oxide powder at high temperature to form glass with FNVD composition, and the glass with FNVD composition is used to make a light window or a photomultiplier tube wall.

In some embodiments, the second sensor 204 includes a photomultiplier tube sensing part for detecting the second radiation, a photovoltaic cell (photovoltaic), a photodiode, and a solar cell.

In some embodiments, the first sensor 202 absorbs the first radiation 206 and emits the second radiation 208. In some embodiments, the second sensor 204 detects the second radiation 208. In some embodiments, the first radiation 206 has a wavelength range shorter than 250 nm. In some embodiments, the first radiation 206 has a wavelength range shorter than 226 nm. In some embodiments, the first radiation 206 has a wavelength range of 30-200 nm. In some embodiments, the first radiation 206 has a wavelength range of 6-24.8 nm. In some embodiments, the first radiation 206 has a wavelength range of 1.03-4.38 nm. In some embodiments, the first radiation 206 has a wavelength range shorter than 10 nm. In some embodiments, the second radiation 208 has a wavelength range of 540-850 nm.

In some embodiments, when the first radiation 206 is absorbed by the first sensor 202, the first sensor 202 converts the first radiation 206 (shorter than 250 nm) into fluorescence with a high quantum conversion efficiency. In some embodiments, the aforementioned quantum conversion efficiency is at least 0.1. In one embodiment, the quantum yield ranges from about 0.1 to about 17. In some embodiments, the spectrum of the second radiation 208 is shown by the second sensor 204 to have a peak at a wavelength of 573-578 nm.

Referring to FIGS. 15A-15C, FIGS. 15A-15C are inductors 300, 400, and 450 according to embodiments of the present invention. The inductors 300, 400, and 450 have a similar structure to that of the inductor 200 in FIG. 14, and the same components are denoted by the same reference numerals, which will not be repeated here. In some embodiments, the sensor 300 further includes a first light window 302 disposed on the first sensor 202. In some embodiments, the sensor 400 further includes a second light window 402 disposed between the first sensor 202 and the second sensor 204. In some embodiments, the sensor 450 further includes a first light window 302 and a second light window 402 at the same time.

Referring to FIG. 16, FIG. 16 is a method 500 for sensing radiation according to an embodiment of the present invention. In some embodiments, the method 500 includes providing a FNVD sensing sheet (step 502); exposing the FNVD sensing sheet to the first radiation (step 504); and generating a spectrum of the second radiation (step 506). The FNVD sensor sheet absorbs the first radiation and generates a second radiation corresponding to the first radiation. For example, the FNVD sensor sheet absorbs a VUV and emits fluorescence of a specific wavelength. For a detailed description of the first radiation absorbed by the FNVD sensing sheet and the second radiation emitted by the FNVD sensing sheet, please refer to the foregoing embodiments of FIGS. 14 and 15A to 15C. In some embodiments, the spectrum of the second radiation generated in step 506 may be, for example, the PL spectrum of FIGS. 3 to 5.

Referring to FIG. 17, FIG. 17 is a lithography apparatus 600 according to an embodiment of the present invention. In some embodiments, the lithography device 600 includes a sensor 608 configured to output a signal. In some embodiments, the sensor 608 can be the sensor described above with reference to FIGS. 14 and 15A to 15C, and can absorb the first radiation 206 and emit the second radiation 208 through the sensor.

In some embodiments, the lithography apparatus 600 further includes a radiation light source 602 that emits radiation 601 to the wafer placed in the lithography apparatus 600. The wafer can be placed on the wafer stage 606 of the chamber 612. In some embodiments, the first radiation 206 emitted by the radiation source 602 is absorbed by the sensor 608. In some embodiments, the radiation 601 emitted by the radiation source 602 may be ultraviolet light (UV), deep ultraviolet light (DUV), extreme ultraviolet light (EUV), vacuum ultraviolet light (VUV), vacuum extreme ultraviolet light or X-rays. . In some embodiments, the radiation source 602 can be a mercury lamp (radiation wavelength is 436nm (G-line) or 365nm (I-line)), krypton fluoride (KrF) excimer laser (radiation wavelength is 248nm), fluorinated Argon (ArF) excimer laser (radiation wavelength is 193nm), fluorine molecule (F ₂ ) excimer laser (radiation wavelength is 157nm), ultraviolet light source with radiation wavelength of 13.5nm. In some embodiments, the lithography apparatus 600 further includes a wafer stage 606 configured to hold wafers. In some embodiments, the wafer has a photosensitive layer that can be patterned by radiation 601 emitted by a radiation source 602 in conjunction with appropriate exposure and development processes.

In some embodiments, the sensor 608 is installed around the wafer stage 606. When the wafer is irradiated by the radiation 601, the sensor 608 can be exposed to and absorb the radiation 601 at the same time, and stimulate another radiation corresponding to the radiation 601 Light, such as a fluorescent light. In some embodiments, the inductor 608 can be integrated with the wafer stage 606. In some embodiments, the sensor 608 may be integrated with the lighting system 604. In some embodiments, the lithography device 600 includes a plurality of sensors 608, which are installed on the periphery of the wafer table 606 and inside the chamber 612, and are configured to receive radiation 601 in different directions, and generate corresponding radiation light, which can be used as quantitative radiation. 601 basis.

In some embodiments, the lithography device 600 further includes a processor 610, and the self-inductor 608 receives the output signal and analyzes and processes it. In some embodiments, the sensor 608 receives the radiation 601 from the radiation source 602 and excites another radiation corresponding to the radiation 601. A sensor module is arranged inside the sensor 608 to detect the corresponding other radiation. The light is converted into a machine-readable signal and sent to the processor 610 for analysis and processing. In some embodiments, the processor 610 generates spectral information based on the signal from the sensor 608. In some embodiments, the processor 610 further includes a display (not shown) for displaying the spectral information generated by the processor 610. In some embodiments, the chamber 612 maintains the wafer in a vacuum environment to perform a lithography process using VUV.

In some embodiments, the lithography apparatus 600 further includes an illumination system 604 configured to adjust the radiation emitted by the radiation source 602. In some embodiments, the lithography apparatus 600 further includes a support structure (not shown) configured to support the patterned device, such as a photomask. The patterned device can be transmissive or reflective, and should be broadly interpreted as including any device that can be used to impart a pattern of radiation to produce a pattern on a target location on the wafer. In some embodiments, a lens system (not shown) is also included, configured to project radiation onto the wafer. In some embodiments, the lens system includes a refractive, reflective, catadioptric, magnetic, electromagnetic, or electrostatic optical system.

This specification and its abstract part only illustrate one or more embodiments of the present invention contemplated by the inventor, and not exhaustively list all the embodiments. This specification and its abstract part shall not be used to limit the scope of patents applied by the applicant.

In the above, there is a way of using blocks to describe the different functions of the different embodiments of the present invention. The boundary delineation between the blocks is only for ease of description. As long as the specified functions and their relative relationships can be properly implemented, there is no need to rigidly abide by the boundaries defined above or in the diagrams.

The description of specific embodiments in this specification can fully expose the general nature of the present invention, so that those skilled in the art can make corresponding, appropriate, and non-conformance to any embodiment for specific application situations without departing from the general spirit of the present invention. Excessive modifications, these modifications still do not depart from the scope of the present invention and its equivalent scope.

The scope of patents applied for in the present invention is defined by the scope of patents applied for later and its equivalent scope, rather than limited by the description, abstract and drawings.

100: manufacturing process steps 102: Step 104: Step 106: step 200: Sensor 202: The first sensor 204: second sensor 206: The First Radiation 208: Second Radiation 300: Sensor 302: first light window 400: Sensor 402: second light window 450: Sensor 500: method 502: Step 504: Step 506: step 600: Lithography equipment 601: Radiation 602: Radiant light source 604: Lighting System 606: Wafer table 608: Sensor 610: processor 612: Chamber

Figure 1 is a schematic diagram of the structure of Fluorescent Nitrogen-Vacancy Diamond (FNVD); Figure 2 shows the photoluminescence (PL) spectrum of FNVD irradiated with 250nm-525nm radiation at a temperature of about 300K; Figure 3 shows the PL spectrum of FNVD irradiated by VUV with a wavelength of 30nm-200nm (6.20eV-41.33eV) at a temperature of about 300K; Figure 4 shows the PL spectrum of FNVD irradiated by EUV with a wavelength of 6nm-24.8nm (50eV-206.8eV) at a temperature of about 300K; Figure 5 shows the PL spectrum of FNVD irradiated by X-rays with wavelengths of 1.03nm-4.38nm (283.07eV-1200eV) at a temperature of about 300K; Figure 6 shows the quantum conversion efficiency of the excitation energy to 1450eV when the FNVD emits fluorescence at a wavelength of 620nm at a temperature of about 300K; Fig. 7 shows the relationship between the intensity of 620nm radiation light and the width of the incident light slit under the irradiation of various wavelengths of radiation of the FNVD; Figure 8 shows (a) the light window (viewport), (b) the polyethylene tape on the light window, and (c) the transmission spectrum of the FNVD powder pasted on the light window through the polyethylene tape; Figure 9 shows the absorption cross section of gaseous oxygen molecules measured at a temperature of about 300K in the wavelength range of 115-200nm using (a) FNVD sensor and (b) sodium salicylate sensor; Figure 10 shows the time decay curve of the fluorescence intensity emitted by the (a) FNVD sensor and (b) the sodium salicylate sensor when irradiated with a wavelength of 60nm radiation; Figure 11 is a diagram showing the relationship between the switch sensor and the fluorescence intensity when the FNVD sensor is irradiated with a wavelength of 60nm radiation at a temperature of about 300K; FIG. 12 shows the steps of the manufacturing process of the FNVD sensor chip according to an embodiment of the present invention; Fig. 13 is a manufacturing process of FNVD powder according to an embodiment of the present invention; Fig. 14 is an inductor according to an embodiment of the present invention; 15A-15C are sensors according to an embodiment of the present invention; FIG. 16 shows the steps of a method for sensing radiation according to an embodiment of the present invention; and Fig. 17 is a lithography apparatus according to an embodiment of the present invention. Note that each drawing is for illustration only, and not for limiting the size, number, ratio, or connection relationship.

200: Sensor

202: The first sensor

204: second sensor

206: The First Radiation

208: Second Radiation

Claims (20)

A Fluorescent Nitrogen-Vacancy Diamond (FNVD) sensor chip, which has a complex nitrogen vacancy center with a concentration of about 1-10000 ppm, and is used to sense first radiation with a wavelength shorter than 200 nm. The FNVD sensing sheet according to claim 1, wherein when the first radiation is absorbed, the FNVD sensing sheet emits second radiation; the second radiation has a wavelength range of 540-850 nm. The FNVD sensing sheet according to claim 2, wherein the spectrum of the second radiation has a peak wavelength at about 573-578 nm. The FNVD sensing sheet according to claim 2, wherein the FNVD sensing sheet converts the first radiation into a fluorescent light with a quantum conversion efficiency of at least 0.1. A method for manufacturing the FNVD sensing sheet according to claim 1, comprising: preparing FNVD powder; and molding the FNVD powder. The manufacturing method of the FNVD sensor sheet according to claim 5, wherein the preparation of the FNVD powder further comprises generating a vacancy defect in the type Ib diamond powder, and diffusing the vacancy defect into the nitrogen in the FNVD powder Around the atom. The manufacturing method of the FNVD sensing sheet according to claim 6, further comprising: annealing the FNVD powder at a temperature of about 600°C to 1000°C. The manufacturing method of the FNVD sensing sheet according to claim 5, further comprising: mixing a filler composed of at least one element or its compound from the following groups in the FNVD powder: molybdenum (Mo), tungsten (W) , Niobium (Nb), tantalum (Ta), rhenium (Re), titanium (Ti), vanadium (V), iron (Fe), cobalt (Co), nickel (Ni), aluminum (Al), zirconium (Zr) , Magnesium (Mg), Calcium (Ca), Cesium (Cs), Silicon (Si), Boron (B). The manufacturing method of the FNVD sensing sheet according to claim 6, further comprising: molding the FNVD powder by pressing, spraying, or heating. The manufacturing method of the FNVD sensing sheet according to claim 9, further comprising: heating the FNVD powder to a temperature between 200°C and 1500°C in an oxygen-deficient environment or in a vacuum. The manufacturing method of the FNVD sensing sheet according to claim 5, further comprising: removing the graphitic carbon on the surface of the FNVD powder. A sensor comprising: a first sensor having a complex nitrogen vacancy center with a concentration of about 1-10000 ppm, configured to absorb first radiation shorter than a wavelength of 200 nm and emit second radiation; and a second sensor, Configured to detect the second radiation. The sensor according to claim 12, wherein the second radiation has a wavelength range of 540-850 nm. The sensor according to claim 12, wherein the second sensor includes a photomultiplier tube, a photocell, a photodiode, or a solar cell. The sensor according to claim 12, wherein when the first radiation is absorbed by the first sensor, the first sensor converts the first radiation into a quantum conversion efficiency of at least 0.1 Fluorescent. A lithography device including a sensor as in claim 12. The lithography device according to claim 16, further comprising a radiation source configured to emit the first radiation. The lithography device according to claim 16, further comprising a processor configured to generate the emission spectrum of the second radiation. A method for sensing radiation, comprising: providing a FNVD sensor sheet as claimed in claim 1, which has a complex nitrogen vacancy center with a concentration of about 1-10000 ppm; exposing the FNVD sensor sheet to a first wavelength shorter than 200 nm Radiation, where the FNVD The sensing sheet emits second radiation corresponding to the first radiation after being exposed to the first radiation; and generates a spectrum of the second radiation. The method according to claim 19, wherein the second radiation has a wavelength range of 540-850 nm.

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