A multi-range hydrogen sensor and decoding method and preparation method thereof

Abstract

The application discloses a multi-range hydrogen sensor and a decoding method and a preparation method thereof in the technical fields of gas sensors, semiconductor gas-sensitive materials, micro-nano manufacturing and hydrogen safety monitoring, and comprises a substrate, a common conductive layer, at least three sensing units and a signal processing module. The multi-range hydrogen sensor and the decoding method and the preparation method thereof can reduce the misjudgment caused by single amplitude determination at the overlapping part of adjacent detection intervals, and improve the stability and anti-drift capability of the output of the boundary interval.

Description

Technical Field

[0001] This invention relates to the fields of gas sensors, semiconductor gas-sensitive materials, micro / nano manufacturing, and hydrogen safety monitoring technology, specifically to a multi-range hydrogen sensor and its decoding and preparation methods. Background Technology

[0002] Hydrogen, as an important clean energy carrier, has been widely used in hydrogen production, storage, transportation, refueling stations, fuel cell vehicles, and related industrial processes. However, hydrogen molecules are small, diffuse rapidly, and have a low ignition energy, posing a risk of combustion and explosion when they reach a certain concentration in the air. Therefore, reliable monitoring is needed for low-concentration leaks, medium-concentration safety warnings, and high-concentration controlled processes.

[0003] Metal oxide semiconductor gas sensors have a solid foundation for hydrogen detection due to their simple structure, low cost, and ease of miniaturization and integration. CuO, as a p-type metal oxide, exhibits resistive response to reducing gases, and its gas-sensing performance can be enhanced through morphological manipulation using nanowires, nanosheets, and thin films. Compared to thin film structures, CuO nanowire arrays possess a higher specific surface area, continuous charge transport paths, and tunable gas diffusion channels, making them a promising candidate for hydrogen sensing.

[0004] However, when dealing with detection over a wide concentration range, a single-structure sensor often struggles to simultaneously achieve low-concentration sensitivity, high-concentration anti-saturation capability, and response speed. While simply stitching multiple sensors into an array can expand the detection coverage, issues such as batch variations, baseline drift, and assembly inconsistencies often arise between different sensors. Furthermore, at the boundaries of adjacent measurement ranges, relying solely on the amplitude of a single resistance response can easily lead to range jumps, misjudgments, or hysteresis.

[0005] On the other hand, existing technologies for adjusting the period, height, or diameter of nanowires are mostly single-parameter optimizations, typically improving only one of the following indicators: sensitivity, response speed, or anti-saturation capability. They lack a unified approach that uses the geometry itself as range encoding information and binds it to decoding rules. Therefore, there is an urgent need for a multi-range hydrogen sensor capable of forming various differentiated CuO nanowire arrays on the same substrate and collaboratively binding the geometry, response parameters, and decision rules. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a multi-range hydrogen sensor, its decoding method and preparation method, which can reduce misjudgment caused by single amplitude judgment at the overlap of adjacent detection intervals and improve the stability and anti-drift capability of the output in the boundary interval.

[0007] To achieve the above objectives, the present invention is implemented using the following technical solution:

[0008] In a first aspect, the present invention provides a multi-range hydrogen sensor, comprising a substrate, a common conductive layer, a signal processing module, and at least three sensing units.

[0009] The sensing unit includes a CuO nanowire array and independent electrodes;

[0010] The common conductive layer is disposed on top of the substrate, the CuO nanowire array is vertically disposed on top of the common conductive layer, the independent electrode is disposed on top of the CuO nanowire array, and the signal processing module is electrically connected to the independent electrode.

[0011] The sensing unit has a geometric coding group defined by the nanowire period P, the nanowire height H and the nanowire diameter D, which is bound to the detection range of the corresponding sensing unit. When the detection ranges are sorted from low to high, the geometric coding groups of two adjacent sensing units are differentiated, including at least two parameters of P, H and D, so that the detection ranges of adjacent sensing units overlap, and different response features are formed within the overlapping range.

[0012] The signal processing module is used to calculate and output the detection range and the final detection value.

[0013] Furthermore, parameter differentiation settings include parameter settings that are incremental or hierarchical.

[0014] The overlap ratio of the overlapping range is 5%-50%; the overlap ratio is the ratio of the overlap width of two adjacent detection intervals to the width of the narrower detection interval.

[0015] Furthermore, the number of sensing units is four, and the geometric coding groups of the four sensing units are as follows:

[0016] First sensing unit: P is 200-300nm, H is 150-170nm, D is 40-42nm;

[0017] Second sensing unit: P is 400-500nm, H is 170-190nm, D is 45-47nm;

[0018] Third sensing unit: P is 600-700nm, H is 190-210nm, D is 50-52nm;

[0019] Fourth sensing unit: P is 800-900nm, H is 210-230nm, and D is 55-57nm.

[0020] Secondly, the present invention provides a decoding method for the multi-range hydrogen sensor, comprising the following steps:

[0021] During testing, the baseline resistance of the i-th sensing unit in the initial sensing unit sequence is collected under a reference atmosphere. Under the atmosphere of the concentration to be measured, when the real-time resistance of the i-th sensing unit reaches the preset steady-state ratio, the response resistance at this time is recorded. And record the response time at this time. , where 1≤i≤n, and n is the total number of sensing units;

[0022] According to the above and Calculate the response resistance parameter of the i-th sensing unit under the measured concentration atmosphere. ;

[0023] Obtain the initial dataset for the i-th sensing unit;

[0024] Based on the initial dataset of the i-th sensing unit, and After normalization, the normalized response resistance parameters of the i-th sensing unit under the measured concentration atmosphere are obtained. and normalized response time ;

[0025] Based on the i-th sensing unit , Normalized response resistance parameter window Normalized response time window Calculate the matching degree A of the i-th sensing unit. i ;

[0026] A i Sort the candidate sensing units in ascending order to obtain a sequence, and select A. i The smallest sensing unit is selected as the candidate decoding unit;

[0027] Perform the first verification step on the candidate decoding unit. If the first verification passes, output the candidate concentration. The measured concentration is used as the actual concentration, and the detection range of the candidate decoding unit is output as the actual measurement range. If the first verification fails, the other adjacent detection unit corresponding to the overlapping range is set as the specific detection unit, and the second verification step is performed on the candidate decoding unit and the specific detection unit.

[0028] If the second verification passes, output As the measured concentration, the detection range of the candidate decoding unit is output as the measured range; otherwise, the next sensing unit in the candidate sensing unit sequence is selected as the candidate decoding unit, and the first verification step is re-executed until the output result is obtained.

[0029] The first verification step includes:

[0030] Based on the target concentration-response resistance parameter mapping curve of the candidate decoding unit and the response resistance parameter of the candidate decoding unit, we obtain ;

[0031] like If the detection range of the candidate decoding unit does not fall within the detection overlap range of the adjacent sensing unit, or is equal to the overlap boundary value, then the first verification passes; otherwise, it fails.

[0032] The second verification step includes:

[0033] Based on the position k of the specific detection unit in the initial sensing unit sequence, obtain the normalized response resistance parameter of the specific detection unit under the atmosphere of the concentration to be measured. and normalized response time ;

[0034] Will Substituting the target concentration-normalized response resistance parameter mapping curve and the target concentration-normalized response time mapping curve of the specific detection unit within the overlapping range, the theoretical normalized response resistance parameter is obtained. and theoretical normalized response time ;

[0035] according to and Calculate the overall trend deviation E of a specific detection unit k The allowable deviation threshold ε for verification of a specific detection unit k For comparison, if E k ≤ε k If yes, the second verification passes; otherwise, the second verification fails.

[0036] Furthermore, the initial dataset of the i-th sensing unit includes the following for the i-th sensing unit: geometric coding group, abnormal drift determination threshold, pre-calibrated mapping curve, pre-calibrated response window, and response trend data of the overlapping range of adjacent sensing units.

[0037] The pre-calibrated mapping curves include: target concentration-response resistance parameter mapping curve, target concentration-response time mapping curve, target concentration-normalized response resistance parameter mapping curve, and target concentration-normalized response time mapping curve.

[0038] The pre-calibrated response window includes: a normalized response resistance parameter window and a normalized response time window;

[0039] The overlap range response trend data of the adjacent sensing units includes:

[0040] Target concentration-normalized response resistance parameter mapping curves of adjacent sensing units in the overlapping range;

[0041] Target concentration-normalized response time mapping curves of adjacent sensing units in the overlapping range;

[0042] Verification allowable deviation threshold for adjacent sensing units.

[0043] Furthermore, the calibration method for the target concentration-response resistance parameter mapping curve, target concentration-response time mapping curve, target concentration-normalized response resistance parameter mapping curve, and target concentration-normalized response time mapping curve of the i-th sensing unit is as follows:

[0044] Define the detection range of the i-th sensing unit And select m concentration values ​​C within the detection interval. M , 1≤M≤m;

[0045] Record the calibration baseline resistance of the i-th sensing unit under the reference atmosphere. And record the i-th sensing unit in C M Calibration response resistance under atmosphere and calibrated response time ;

[0046] according to and Calculate the value of the i-th sensing unit in C. M Calibration response resistance parameters under different atmospheres The calculation formula is:

[0047] ;

[0048] Will and the corresponding C M By fitting the data, the target concentration-response resistance parameter mapping curve of the i-th sensing unit is obtained. ,in, S is the target concentration-response resistance parameter mapping function. i Let C be the calibration response resistance parameter of the i-th sensing unit, and C be a formal parameter representing the concentration, satisfying... ;

[0049] Will After normalization, the value of the i-th sensing unit in C is obtained. M Normalized calibration response resistance parameters under different atmospheres The calculation formula is:

[0050] ;

[0051] Among them, S i,minFor S i Minimum value, S i,max For S i Maximum value;

[0052] Will and the corresponding C M By fitting the data, the target concentration-normalized response resistance parameter mapping curve of the i-th sensing unit is obtained. ,in, Let X be the target concentration-normalized response resistance parameter mapping function. i The normalized calibration response resistance parameter is set for the i-th sensing unit;

[0053] Will and the corresponding C M By fitting the data, the target concentration-response time mapping curve of the i-th sensing unit is obtained. ,in, Let T be the target concentration-response time mapping function. i Let be the calibration response time of the i-th sensing unit;

[0054] Will After normalization, the value of the i-th sensing unit in C is obtained. M Normalized calibration response time under different atmospheres The calculation formula is:

[0055] ;

[0056] Among them, T i,min For T i Minimum value, T i,max For T i Maximum value;

[0057] Will and the corresponding C M By fitting the data, the target concentration-normalized response time mapping curve of the i-th sensing unit is obtained. ,in, Y is the target concentration-normalized response time mapping function. i The normalized calibration response time for the i-th sensing unit;

[0058] The calibration method for the normalized response resistance parameter window and the normalized response time window of the i-th sensing unit is as follows:

[0059] Select S i Within the range of values, the minimum calibrated response resistance parameter that meets the preset signal-to-noise ratio requirement. ,calculate The corresponding normalized calibrated response resistance parameter a i and according to exist Find the corresponding concentration C a According to C a exist Find the corresponding normalized calibration response time c. i ;

[0060] Select The above refers to the calibration response resistance parameter corresponding to the differential slope decreasing to the preset slope. ,calculate The corresponding normalized calibrated response resistance parameter b i and according to exist Find the corresponding concentration C b According to C b exist Find the corresponding normalized calibration response time d. i ;

[0061] Obtain the normalized response resistance parameter window and normalized response time window ;

[0062] The method for determining the verification allowable deviation threshold of the adjacent sensing units includes:

[0063] Obtain the position j of the adjacent sensing unit in the initial sensing unit sequence, 1≤j≤n;

[0064] Select one known concentration value C within the detection interval. L , 1≤L≤l;

[0065] Record adjacent sensing units at C L Response resistance under atmosphere and calibrated response time ;

[0066] according to and Calculate the adjacent sensing units in C L Response resistance parameters under different atmospheres The calculation formula is:

[0067] ;

[0068] Will Normalization is performed to obtain the values ​​of adjacent sensing units in C. L Normalized response resistance parameters under different atmospheres The calculation formula is:

[0069] ;

[0070] Will Normalization is performed to obtain the values ​​of adjacent sensing units in C. L Normalized response time under different atmospheres The calculation formula is:

[0071] ;

[0072] according to , Adjacent sensing units in C L Theoretical normalized response resistance parameters under different atmospheres and adjacent sensing units in C L Theoretical normalized response time under atmosphere Calculate the comprehensive residual sequence The calculation formula is:

[0073] ;

[0074] in, Here, η is the weighting coefficient for the normalized response resistance parameter, and η is the weighting coefficient for the normalized response time. ;

[0075] Will Sort by numerical value and use a preset percentage quantile as the verification allowable deviation threshold ε for adjacent sensing units. j ;

[0076] The formation of different response characteristics includes the formation of different target concentration-normalized response resistance parameter mapping curves and target concentration-normalized response time mapping curves.

[0077] Furthermore, the aforementioned Calculated using the following formula:

[0078] ;

[0079] The Calculated using the following formula:

[0080] ;

[0081] The Calculated using the following formula:

[0082] ;

[0083] The A i Calculated using the following formula:

[0084] ;

[0085] In the formula, For window distance function, , ;

[0086] when Located in [a i ,b i [Inner time,] ;when hour, ;when hour, ;

[0087] when Located in [c i ,d i [Internal Time] ;when hour, ;when hour, ;

[0088] α and β are both weighting coefficients, and α + β = 1;

[0089] The overall trend deviation E k Calculated using the following formula:

[0090] ;

[0091] In the formula, γ+δ=1, where γ is the weighting coefficient of the response resistance parameter and δ is the weighting coefficient of the response time.

[0092] Furthermore, when the baseline resistance drift of any sensing unit exceeds a preset drift threshold, an alarm and a device replacement prompt will be output.

[0093] Thirdly, the present invention provides a method for preparing the multi-range hydrogen sensor, comprising the following steps:

[0094] A common conductive layer and an Al film are sequentially deposited on the substrate surface;

[0095] According to the preset P, cover and protect the Al film, expose the preset sensing unit forming areas on the Al film one by one, selectively anodize the exposed sensing unit forming areas to form AAO template areas, and cover and protect the already formed AAO template areas before exposing the next sensing unit forming area to obtain the first-processed AAO template area.

[0096] Based on the preset H, the barrier layer of AAO template regions with different P is thinned to obtain the secondary processed AAO template regions.

[0097] According to the preset D, the AAO template area with H is subjected to hole opening and secondary hole expansion processing to obtain the AAO template area with three processing steps.

[0098] Copper nanowires were electrodeposited in the open area of ​​the AAO template region after three treatments, and the height of the nanowires in different regions was controlled by adjusting the electrodeposition time so that the final height was the same as the preset H.

[0099] After removing the AAO template, copper nanowires were subjected to an oxidation heat treatment to obtain a CuO nanowire array.

[0100] Independent electrodes were fabricated and then cut, bonded, and packaged to obtain the final multi-range hydrogen sensor.

[0101] Furthermore, before sequentially depositing the common conductive layer and the Al film on the substrate surface, the substrate needs to be pretreated.

[0102] A partitioned photolithography mask process is used to selectively anodize the exposed sensor unit formation area;

[0103] The selective anodizing process uses a phosphoric acid electrolyte, with an anodizing voltage of 45-200V and an anodizing time of 20-90min.

[0104] The barrier layer thinning adopts a stepped pressure-reducing anodizing process, and the opening and secondary pore expansion adopt a 5% phosphoric acid solution with a pore expansion time of 10-30 min.

[0105] The thickness of the common conductive layer is 50-100 nm, and the thickness of the Al film is 3-4 μm;

[0106] The oxidation heat treatment temperature is 300-350℃, and the holding time is 2-4h.

[0107] Compared with the prior art, the beneficial effects achieved by the present invention are as follows:

[0108] The multi-range hydrogen sensor, its decoding method, and its preparation method provided by this invention use the nanowire period P, nanowire height H, and nanowire diameter D as a geometric coding group to define the sensing unit. This allows the structural parameters to become the coding information for concentration range identification, enabling each sensing unit to form a distinguishable response characteristic. Compared with a single parameter adjustment scheme, this method expands the detection range while taking into account both low-concentration sensitivity and high-concentration anti-saturation capability.

[0109] The multi-range hydrogen sensor, its decoding method, and its fabrication method provided by this invention calculate the matching degree based on the response resistance parameter, response time, normalized response resistance parameter window, and normalized response time window of the sensing unit, obtain candidate decoding units, and verify the candidate concentration of the candidate decoding units. This can reduce misjudgments caused by single-amplitude judgment at the overlapping of adjacent detection intervals and improve the stability and anti-drift capability of the output in the boundary interval. Attached Figure Description

[0110] Figure 1 This is a schematic diagram of the overall structure of the multi-range hydrogen sensor provided in an embodiment of the present invention;

[0111] Figure 2 This is a partial cross-sectional schematic diagram of a multi-range hydrogen sensor provided in an embodiment of the present invention;

[0112] Figure 3 This is a schematic diagram of the structure of a sensing unit with different geometric coding groups provided in an embodiment of the present invention;

[0113] Figure 4 The interval determination accuracy-concentration curves of the determination results of the decoding method and the single maximum response amplitude determination method provided in the embodiments of the present invention in adjacent overlapping ranges are shown, wherein (a) is the single maximum response amplitude determination method and (b) is the decoding method provided in the embodiments of the present invention.

[0114] Figure 5 This is a comparison chart of the measured performance of the encoding scheme provided in the embodiments of the present invention with that of a single-parameter differentiated or non-encoded array scheme.

[0115] In the figure: 1. Substrate; 2. Common conductive layer; 3. CuO nanowire array; 4. Independent electrode; 5. Isolation region; 6-1. First sensing unit; 6-2. Second sensing unit; 6-3. Third sensing unit; 6-4. Fourth sensing unit. Detailed Implementation

[0116] The present invention will be further described below with reference to the accompanying drawings. The following embodiments are only used to more clearly illustrate the technical solution of the present invention, and should not be used to limit the scope of protection of the present invention.

[0117] Example 1: This example provides a multi-range hydrogen sensor, such as... Figure 1 As shown, the sensor includes: a substrate 1, a common conductive layer 2, at least three sensing units, and a signal processing module. In this embodiment, the sensing units include a first sensing unit 6-1, a second sensing unit 6-2, a third sensing unit 6-3, and a fourth sensing unit 6-4, arranged sequentially from left to right. In this embodiment, the multi-range hydrogen sensor also includes an isolation region 5, disposed between the sensing units, to reduce the mutual influence caused by electrical crosstalk and lateral gas diffusion. The effective response area of ​​each sensing unit can be 0.05 mm²-1 mm², preferably 0.5 mm².

[0118] The sensing unit includes a CuO nanowire array 3 and an independent electrode 4.

[0119] The common conductive layer 2 is disposed on the top of the substrate 1. The CuO nanowire array 3 is parallel to each other and is disposed on the top of the common conductive layer 2 perpendicular to the common conductive layer 2. The independent electrode 4 is disposed on the top of the CuO nanowire array 3 and is electrically connected to the CuO nanowire array 3 to form each sensing unit. The signal processing module is electrically connected to each sensing unit through the independent electrode 4.

[0120] The substrate 1 can be a silicon substrate, a glass substrate, or a ceramic substrate, preferably a single-crystal silicon substrate. The common conductive layer 2 can be an Au, Pt, Ti / Au, or Cr / Au conductive layer. The common conductive layer 2 serves as both a common bottom electrode for each sensing unit and a conductive support layer in the subsequent electrodeposition process.

[0121] The sensing unit has a geometric code group defined by the nanowire period P, the nanowire height H, and the nanowire diameter D, which serves as a structured range identifier for the corresponding sensing unit. When sorted according to the detection range from low to high, the geometric code groups of two adjacent sensing units are differentiated, including at least two parameters of P, H, and D, so that the detection ranges of adjacent sensing units overlap, and different response characteristics are formed within the overlapping range.

[0122] The signal processing module includes a multi-channel resistance acquisition unit, a storage unit, and a decision unit;

[0123] The multi-channel resistance acquisition unit is used to acquire the baseline resistance, response resistance, and response time of each sensing unit;

[0124] The storage unit is used to store the initial dataset of each sensing unit;

[0125] The determination unit is used to select the decoding sensing unit based on the initial dataset, baseline resistance, response resistance, and response time, and to calculate and output the corresponding detection range and the final detection value.

[0126] In this embodiment, the initial dataset of the i-th sensing unit includes the i-th sensing unit's: geometric coding group, abnormal drift determination threshold, pre-calibrated mapping curve, pre-calibrated response window, and response trend data of the overlapping range of adjacent sensing units, where 1≤i≤n, and n is the total number of sensing units.

[0127] The pre-calibrated mapping curves include: target concentration-response resistance parameter mapping curve, target concentration-response time mapping curve, target concentration-normalized response resistance parameter mapping curve, and target concentration-normalized response time mapping curve.

[0128] The pre-calibrated response window includes: a normalized response resistance parameter window and a normalized response time window;

[0129] The overlap range response trend data of the adjacent sensing units includes:

[0130] Target concentration-normalized response resistance parameter mapping curves of adjacent sensing units in the overlapping range;

[0131] Target concentration-normalized response time mapping curves of adjacent sensing units in the overlapping range;

[0132] Verification allowable deviation threshold for adjacent sensing units.

[0133] The calibration method for the target concentration-response resistance parameter mapping curve, target concentration-response time mapping curve, target concentration-normalized response resistance parameter mapping curve, and target concentration-normalized response time mapping curve of the i-th sensing unit is as follows:

[0134] Define the detection range of the i-th sensing unit. And select m concentration values ​​C within the detection interval. M , 1≤M≤m;

[0135] Record the calibration baseline resistance of the i-th sensing unit under the reference atmosphere. And record the i-th sensing unit in C M Calibration response resistance under atmosphere and calibrated response time ;

[0136] according to and Calculate the value of the i-th sensing unit in C. M Calibration response resistance parameters under different atmospheres The calculation formula is:

[0137] ;

[0138] Will and the corresponding C M By fitting the data, the target concentration-response resistance parameter mapping curve of the i-th sensing unit is obtained. ,in, S is the target concentration-response resistance parameter mapping function. i Let C be the calibration response resistance parameter of the i-th sensing unit, and C be a formal parameter representing the concentration, satisfying... ;

[0139] Will After normalization, the value of the i-th sensing unit in C is obtained. M Normalized calibration response resistance parameters under different atmospheres The calculation formula is:

[0140] ;

[0141] Among them, S i,min For S i Minimum value, S i,max For S i Maximum value;

[0142] Will and the corresponding C M By fitting the data, the target concentration-normalized response resistance parameter mapping curve of the i-th sensing unit is obtained. ,in, Let X be the target concentration-normalized response resistance parameter mapping function. i The normalized calibration response resistance parameter is set for the i-th sensing unit;

[0143] Will and the corresponding C M By fitting the data, the target concentration-response time mapping curve of the i-th sensing unit is obtained. ,in, Let T be the target concentration-response time mapping function. i Let be the calibration response time of the i-th sensing unit;

[0144] Will After normalization, the value of the i-th sensing unit in C is obtained. M Normalized calibration response time under different atmospheres The calculation formula is:

[0145] ;

[0146] Among them, T i,min For T i Minimum value, T i,max For T i Maximum value;

[0147] Will and the corresponding C M By fitting the data, the target concentration-normalized response time mapping curve of the i-th sensing unit is obtained. ,in, Y is the target concentration-normalized response time mapping function. i The normalized calibration response time for the i-th sensing unit;

[0148] The calibration method for the normalized response resistance parameter window and the normalized response time window of the i-th sensing unit is as follows:

[0149] Select S i Within the range of values, the minimum calibrated response resistance parameter that meets the preset signal-to-noise ratio requirement. ,calculate The corresponding normalized calibrated response resistance parameter a i and according to exist Find the corresponding concentration C a According to C a exist Find the corresponding normalized calibration response time c. i ;

[0150] Select The above refers to the calibration response resistance parameter corresponding to the differential slope decreasing to the preset slope. ,calculate The corresponding normalized calibrated response resistance parameter b i and according to exist Find the corresponding concentration C b According to C b exist Find the corresponding normalized calibration response time d. i ;

[0151] Obtain the normalized response resistance parameter window and normalized response time window ;

[0152] The method for determining the verification allowable deviation threshold of the adjacent sensing units includes:

[0153] Let the adjacent sensing unit be the j-th sensing unit, where 1≤j≤n;

[0154] Select one known concentration value C within the detection interval. L , 1≤L≤l;

[0155] Record the j-th sensing unit in C L Response resistance under atmosphere and calibrated response time ;

[0156] according to and Calculate the adjacent sensing units in C L Response resistance parameters under different atmospheres The calculation formula is:

[0157] ;

[0158] Will After normalization, the value of the j-th sensing unit in C is obtained. L Normalized response resistance parameters under different atmospheres The calculation formula is:

[0159] ;

[0160] Will After normalization, the value of the j-th sensing unit in C is obtained. L Normalized response time under different atmospheres The calculation formula is:

[0161] ;

[0162] according to , The j-th sensing unit in C L Theoretical normalized response resistance parameters under different atmospheres and the j-th sensing unit in C L Theoretical normalized response time under atmosphere Calculate the comprehensive residual sequence The calculation formula is:

[0163] ;

[0164] in, Here, η is the weighting coefficient for the normalized response resistance parameter, and η is the weighting coefficient for the normalized response time. ;

[0165] Will Sort by numerical value and take the 95th percentile value as the verification tolerance threshold ε for the j-th sensing unit. j .

[0166] The detection intervals of the adjacent sensing units overlap, and within the overlapping range, different response characteristics are formed, including different target concentration-normalized response resistance parameter mapping curves and target concentration-normalized response time mapping curves.

[0167] In this embodiment, when sorting the detection intervals from low to high, the geometric coding groups of at least two adjacent sensing units are differentiated, including setting the P, H and D of the corresponding geometric coding groups to be incremental or hierarchically incremental.

[0168] The detection intervals of the adjacent sensing units overlap, wherein the overlap ratio is 5%-50%, preferably 10%-30%; the overlap ratio is the ratio of the overlap width of two adjacent detection intervals to the width of the narrower detection interval.

[0169] The first sensing unit 6-1, the second sensing unit 6-2, the third sensing unit 6-3, and the fourth sensing unit 6-4 provided in this embodiment have the following geometric coding groups:

[0170] First sensing unit 6-1: P is 200-300nm, H is 150-170nm, D is 40-42nm;

[0171] Second sensing unit 6-2: P is 400-500nm, H is 170-190nm, D is 45-47nm;

[0172] Third sensing unit 6-3: P is 600-700nm, H is 190-210nm, D is 50-52nm;

[0173] The fourth sensing unit 6-4: P is 800-900nm, H is 210-230nm, and D is 55-57nm.

[0174] The geometric coding groups and target detection intervals of the four sensing units are shown in Table 1.

[0175] Table 1

[0176]

[0177] After pre-calibration, the target detection range, normalized response resistance parameter window, and normalized response time window of the four sensing units are shown in Table 2.

[0178] Table 2

[0179]

[0180] The window values ​​in Table 2 are exemplary values ​​obtained through pre-calibration in this embodiment. In specific applications, they can be recalibrated based on the test atmosphere, target alarm threshold, and environmental conditions. Each window is only used for the final concentration range output when it is simultaneously bound to the corresponding geometric coding group and adjacent trend rules.

[0181] In Table 1, P, H, and D are not arbitrary sizes, but rather used to form a geometric coding group bound to the target detection interval. For any sensing unit, a valid geometric coding group in the sense of this invention is only formed when its P, H, and D combination, together with the corresponding target detection interval, the two-parameter response window (normalized response resistance parameter window and normalized response time window), and the overlapping range response trend data, are calibrated. Changing any parameter of P, H, or D individually, or simply setting up multiple sensors of different sizes side by side, cannot replace the coding method of this invention.

[0182] The detection ranges described above are recommended calibration results in the embodiments. In practical applications, the low-concentration leak alarm threshold, safety warning threshold, and high-concentration process monitoring threshold can be redefined according to the target application scenario, and the target concentration range and dual-parameter response window corresponding to each geometric coding group can be updated through calibration experiments. For the detection of hydrogen concentrations above the lower explosive limit in air, this invention is mainly used for concentration monitoring in inert atmospheres, low-oxygen environments, or controlled process gases; when used for leak alarms, low-concentration and medium-low-concentration geometric coding units can be prioritized for safety warnings.

[0183] In this embodiment, the preset steady-state ratio is 90%, the preset signal-to-noise ratio requirement means that the signal-to-noise ratio S / N≥3, the preset slope is 20% of the maximum differential slope of the corresponding mapping curve, the preset ratio quantile is 95%, and the abnormal drift judgment threshold is 10%.

[0184] In this embodiment, α=0.7 and β=0.3 in the matching degree calculation, γ=0.6 and δ=0.4 in the comprehensive trend deviation calculation, and in the comprehensive residual sequence calculation... =0.6, η=0.4; the verification allowable deviation thresholds for the first sensing unit 6-1, the second sensing unit 6-2, the third sensing unit 6-3 and the fourth sensing unit 6-4 are ε1=0.12, ε2=0.12, ε3=0.15 and ε4=0.18, respectively.

[0185] In the low-concentration range, smaller wire diameter and shorter period help increase the proportion of surface active sites per unit volume, making the resistance response more sensitive to low-concentration hydrogen gas. In the high-concentration range, larger period, larger wire diameter, and taller nanowire structure help improve the gas diffusion channels inside the array and delay response saturation. By synergistically varying the three parameters P, H, and D, rather than by independently varying a single geometric parameter, sensing units with response characteristics in the detection range can be formed on the same substrate 1, providing a distinguishable data basis for subsequent decoding.

[0186] Example 2: This example provides a decoding method for the multi-range hydrogen sensor provided in Example 1, including the following steps:

[0187] During testing, the baseline resistance of the i-th sensing unit under a reference atmosphere is collected. Under the atmosphere of the concentration to be measured, when the real-time resistance of the i-th sensing unit reaches the preset steady-state ratio, the response resistance at this time is recorded. And record the response time at this time. ;

[0188] According to the above and Calculate the response resistance parameter of the i-th sensing unit under the measured concentration atmosphere. ;

[0189] Obtain the initial dataset for the i-th sensing unit;

[0190] Based on the initial dataset of the i-th sensing unit, and After normalization, the normalized response resistance parameters of the i-th sensing unit under the measured concentration atmosphere are obtained. and normalized response time ;

[0191] Based on the i-th sensing unit , Normalized response resistance parameter window Normalized response time window Calculate the matching degree A of the i-th sensing unit. i ;

[0192] A i Sort the candidate sensing units in ascending order to obtain a sequence, and select A. i The smallest sensing unit is selected as the candidate decoding unit;

[0193] Perform the first verification step on the candidate decoding unit. If the first verification passes, output the candidate concentration. The measured concentration is used as the actual concentration, and the detection range of the candidate decoding unit is output as the actual measurement range. If the first verification fails, the other adjacent detection unit corresponding to the overlapping range is set as the specific detection unit, and the second verification step is performed on the candidate decoding unit and the specific detection unit.

[0194] If the second verification passes, output As the measured concentration, the detection range of the candidate decoding unit is output as the measured range; otherwise, the next sensing unit in the candidate sensing unit sequence is selected as the candidate decoding unit, and the first verification step is re-executed until the output result is obtained.

[0195] The first verification step includes:

[0196] Based on the target concentration-response resistance parameter mapping curve of the candidate decoding unit and the response resistance parameter of the candidate decoding unit, we obtain ;

[0197] like If the detection range of the candidate decoding unit does not fall within the detection overlap range of the adjacent sensing unit, or is equal to the overlap boundary value, then the first verification passes; otherwise, the other detection unit corresponding to the overlap range is designated as the specific detection unit, and a second verification step is performed on the candidate decoding unit. If the second verification passes, the output is... The actual measured concentration is used as the reference; otherwise, the first verification is considered to have failed.

[0198] The second verification step includes:

[0199] Suppose that the normalized response resistance parameter of a specific detection unit under the atmosphere of the concentration to be measured is obtained based on the position k of the specific detection unit in the initial sensing unit sequence. and normalized response time ;

[0200] Will Substituting the target concentration-normalized response resistance parameter mapping curve and the target concentration-normalized response time mapping curve of the specific detection unit within the overlapping range, the theoretical normalized response resistance parameter is obtained. and theoretical normalized response time ;

[0201] according to and Calculate the overall trend deviation E of a specific detection unit k The allowable deviation threshold ε for verification of a specific detection unit k For comparison, if E k ≤ε k If yes, the second verification passes; otherwise, the second verification fails.

[0202] Among them, the Calculated using the following formula:

[0203] ;

[0204] The Calculated using the following formula:

[0205] ;

[0206] The Calculated using the following formula:

[0207] ;

[0208] The A i Calculated using the following formula:

[0209] ;

[0210] In the formula, For window distance function, , ;

[0211] when Located in [a i ,b i [Inner time,] ;when hour, ;when hour, ;

[0212] when Located in [c i ,d i [Internal Time] ;when hour, ;when hour, ;

[0213] α and β are both weighting coefficients, and α+β=1. The value of α ranges from 0.5 to 0.8, and the value of β ranges from 0.2 to 0.5.

[0214] The overall trend deviation E k Calculated using the following formula:

[0215] ;

[0216] Where γ+δ=1, γ is the weighting coefficient of the response resistance parameter, and δ is the weighting coefficient of the response time.

[0217] In this embodiment, when the baseline resistance drift of any sensing unit exceeds a preset drift threshold, an alarm and a device replacement prompt are output.

[0218] In this embodiment, the detection range of each sensing unit is pre-calibrated. The calibration method is as shown in Embodiment 1. The calibration atmosphere may include inert carrier gas or low-oxygen background gas. For leak alarm applications, air background calibration can also be performed on the low concentration range under safe conditions.

[0219] To verify the effectiveness of the decoding method provided in this embodiment, it is compared with the existing method for determining the amplitude of a single maximum resistance response. The test method is as follows:

[0220] Using N2 as the background carrier gas, different concentrations of detection atmospheres were prepared for testing using a standard H2 / N2 gas mixture (accuracy ±2%); the test temperature was 25±2℃.

[0221] Five test concentration points were evenly selected in each of the three overlapping ranges of 10-20 vol%H2, 30-40 vol%H2, and 60-70 vol%H2. At least three samples were used to test each concentration point, and each sample was tested repeatedly at least five times.

[0222] The single maximum resistance response amplitude determination method and the decoding method provided in Embodiment 2 of the present invention are used respectively to decode and obtain the determination result, including the determination concentration and the determination range.

[0223] The interval determination accuracy of the two methods is used as the evaluation index. The interval determination accuracy is the proportion of the number of tests in which the determination interval output by each method matches the actual interval to which the test concentration point belongs.

[0224] Test results are as follows Figure 4 As shown, Figure 4 The interval determination accuracy-concentration curves of the determination results of the decoding method and the single maximum response amplitude determination method provided in Embodiment 2 of the present invention in adjacent overlapping ranges are shown, where (a) is the single maximum response amplitude determination method and (b) is the decoding method provided in the embodiment of the present invention. Figure 4 This indicates that the decoding method provided by the present invention has a lower boundary false positive rate than the single frame value determination method within the overlapping concentration range of the detection interval.

[0225] Under the above test conditions, the four sensing units provided in Example 1 exhibit superior response characteristics within their recommended detection ranges. The first sensing unit 6-1 is suitable for detection in the low concentration range, the second sensing unit 6-2 is suitable for detection in the low to medium concentration range, the third sensing unit 6-3 is suitable for detection in the medium to high concentration range, and the fourth sensing unit 6-4 is suitable for detection in the high concentration range.

[0226] The multi-range hydrogen sensor provided in Example 1 was used as the experimental group, and tests were performed on both the experimental group and the control group. The control group contained four sensing units, and the control group was set up as follows:

[0227] Control group 1 only changed P; H and D were fixed, specifically: H=190nm, D=46nm, and the period P was set to 200-300nm, 400-500nm, 600-700nm, and 800-900nm respectively.

[0228] Control group 2 only changed D; P and H were fixed, specifically: P=500nm, H=190nm, and the line diameter D was set to 40-42nm, 45-47nm, 50-52nm, and 55-57nm respectively.

[0229] In control group 3, only H was changed; P and D were fixed, specifically: P=500nm, D=46nm, and the height H was set to 150-170nm, 170-190nm, 190-210nm, and 210-230nm respectively.

[0230] Control group 4: The same multi-range hydrogen sensor as the experimental group was used, but the pre-calibration method adopted was a conventional calibration method in the field;

[0231] Control group 5: The same multi-range hydrogen sensor as the experimental group was used, but the second verification step was omitted in the decoding process, and the first verification step was modified as follows:

[0232] Based on the target concentration-response resistance parameter mapping curve of the candidate decoding unit and the response resistance parameter of the candidate decoding unit, the candidate concentration is obtained. ;

[0233] like If the detection range of the candidate decoding unit does not fall within the detection overlap range of its adjacent sensing units, or is equal to the overlap boundary value, then the first verification passes, and the output is generated. As the measured concentration, the detection range of the candidate decoding unit is output;

[0234] like If the value falls within the aforementioned overlapping range (and is not equal to the overlapping boundary value), then the response resistance parameter of the candidate decoding unit is obtained by reverse lookup based solely on the target concentration-response resistance parameter mapping curve of the candidate decoding unit. It is directly used as the measured concentration output, and the detection range of the candidate decoding unit is also output.

[0235] For the experimental group and each control group, test concentration points were uniformly selected within the full range, and tests were performed N times. The full-range determination accuracy was used as an indicator to verify the beneficial effects of the encoding and decoding method of this invention, wherein:

[0236] Full-range accuracy is the percentage of times the concentration range output by the decoder matches the actual concentration range out of the total number of tests.

[0237] For the experimental group and each control group, test concentration points were uniformly selected within the overlapping range, and the tests were performed N times. The boundary misjudgment rate was used as an indicator to verify the beneficial effect of the encoding and decoding method of the present invention, wherein the boundary misjudgment rate is the proportion of the number of times the output erroneous concentration interval is counted to the total number of tests.

[0238] Experimental results are as follows Figure 5 As shown, in control groups 1-3, when P, H, and D are adjusted using a single parameter, the full-range judgment accuracy is lower than that of the experimental group, while the boundary misjudgment rate is higher than that of the experimental group. In control groups 4-5, when different encoding or decoding methods are used, the experimental group also shows better comprehensive judgment performance, indicating that the present invention is not a simple superposition of known nanostructure optimization, known sensor array, or conventional threshold algorithm.

[0239] The experimental group of this invention coordinates the array gaps, effective surface area, and diffusion paths formed by P, H, and D to enable different sensing units to form distinguishable response amplitude-response time trajectories; then, through dual-parameter windowing and adjacent trend verification, these trajectories are converted into concentration range outputs. This closed-loop design from structure encoding to trend decoding demonstrates the substantial technical contribution of this scheme.

[0240] The above measured data, control design, and effect descriptions are used to illustrate the technical effects of the present invention and should not be construed as limiting the scope of protection. For different application scenarios, the dual-parameter window, trend rules, and weighting coefficients can be recalibrated based on the actual concentration range, alarm threshold, test atmosphere, and environmental conditions.

[0241] Example 3 illustrates a method for preparing a single-substrate 1-partition AAO for the multi-range hydrogen sensor provided in Example 1.

[0242] Step 1, Pretreatment of Substrate 1. A 4-inch single-crystal silicon wafer was selected as substrate 1. The natural oxide layer on the surface was removed using hydrofluoric acid solution, followed by cleaning with acetone, anhydrous ethanol and deionized water, and then dried with high-purity nitrogen gas.

[0243] Step 2, functional film deposition. A common conductive layer 2 and an Al film are deposited on the surface of substrate 1 using magnetron sputtering. The common conductive layer 2 can be Au, Pt, Ti / Au, or Cr / Au, with a thickness of 50-100 nm, preferably 80 nm; the Al film thickness can be 3-4 μm, preferably 3.5 μm.

[0244] Step 3, selective anodizing by region. A region-specific photolithography masking process is used, exposing only one Al film region to be formed into the sensing unit at a time, while the remaining regions are covered and protected by photoresist or electrolyte-resistant masking material. Selective anodizing is performed on the exposed regions to form AAO template regions with the target nanopore period P. Anodizing can be performed using a phosphoric acid electrolyte, with the temperature controlled at 0-5℃, the anodizing voltage at 45-200V, and the anodizing time at 20-90min. The anodizing conditions for different regions are independently set according to the target P value, ensuring that the template pore period corresponds to the geometric coding group.

[0245] Step 4: Protection of the Formed Template Area. After completing each AAO template area, an acid- and alkali-resistant protective layer is applied to cover and protect the formed AAO template area. This protective layer covers at least the orifice and boundary areas of the AAO template area to prevent subsequent anodizing, electrolyte wetting, or hole opening / enlargement processes from altering the hole period and diameter of the formed AAO template area. This step is crucial for achieving stable fabrication of multiple geometrically encoded regions on the same substrate, preventing damage to the formed template area from subsequent region processing.

[0246] Step 5, repeat the partitioned anodizing process. Repeat the partitioned exposure, selective anodizing, and pre-formed area protection steps until multiple AAO template regions with different nanopore periods P are formed on the same substrate 1. Different AAO template regions correspond to different target detection intervals.

[0247] Step Six: Barrier Layer Thinning, Pore Opening, and Secondary Pore Enlargement. Barrier layer thinning, pore opening, and secondary pore enlargement are performed on each AAO template region. Barrier layer thinning can be achieved using a stepped-down anodizing process; pore opening and secondary pore enlargement can be performed using a 5% (w / w) phosphoric acid solution for 10-30 min. Nanopores with different diameters (D) are obtained by adjusting the pore enlargement time.

[0248] Step 7, Copper Nanowire Electrodeposition. Using the common conductive layer 2 as the cathode conductive support and a platinum sheet as the anode, constant current electrodeposition is performed in a copper-containing electrolyte. The height H of the copper nanowire is adjusted by controlling the electrodeposition time in different regions, so that P, H, and D together form a three-parameter geometric coding group corresponding to the target detection interval. Examples of the partitioned AAO process parameters for the four sensing units are shown in Table 3.

[0249] Table 3

[0250]

[0251] The parameters listed in Table 3 are used to illustrate the compatibility relationships of different geometric coding groups. Among them, the anodic oxidation voltage and the pore expansion time mainly affect P and D, respectively, and the electrodeposition control target is mainly used to adjust the height H of the nanowire. In actual preparation, the parameters can be finely adjusted within the above range according to the template morphology test results.

[0252] Step 8: Template Removal and Oxidation Treatment. After removing the AAO template, the copper nanowires are subjected to an oxidation heat treatment in air or an oxygen-containing atmosphere to form a CuO nanowire array 3. The oxidation heat treatment temperature can be 300-350℃, and the holding time is 2-4h. Subsequently, independent electrodes 4 are fabricated, and cutting, bonding, and encapsulation are completed to obtain a multi-range hydrogen sensor with a CuO nanowire array 3 on the same substrate.

[0253] In the description of this invention, it should be understood that the terms "center," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," and "outer," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only used to explain the relative positional relationship and movement between components in a specific posture. If the specific posture changes, the directional indication will also change accordingly. They are used only for the convenience of describing the invention and for simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on the invention. Furthermore, the terms "first," "second," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, features defined with "first," "second," etc., may explicitly or implicitly include one or more of that feature. In the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0254] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "installation," "connection," and "linking" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium; and they can refer to the internal connection of two components. Those skilled in the art will understand the specific meaning of the above terms in this invention based on the specific circumstances.

[0255] The embodiments of the present invention have been described above with reference to the accompanying drawings. However, the present invention is not limited to the specific embodiments described above. The specific embodiments described above are merely illustrative and not restrictive. Those skilled in the art can make many other forms under the guidance of the present invention without departing from the spirit and scope of the claims. All of these forms are within the protection scope of the present invention.

Claims

1. A multi-range hydrogen sensor, characterized in that, It includes a substrate, a common conductive layer, a signal processing module, and at least three sensing units; The sensing unit includes a CuO nanowire array and independent electrodes; The common conductive layer is disposed on top of the substrate, the CuO nanowire array is vertically disposed on top of the common conductive layer, the independent electrode is disposed on top of the CuO nanowire array, and the signal processing module is electrically connected to the independent electrode. The sensing unit has a geometric coding group defined by the nanowire period P, the nanowire height H and the nanowire diameter D, which is bound to the detection range of the corresponding sensing unit. When the detection ranges are sorted from low to high, the geometric coding groups of two adjacent sensing units are differentiated, including at least two parameters of P, H and D, so that the detection ranges of adjacent sensing units overlap, and different response features are formed within the overlapping range. The signal processing module is used to calculate and output the detection range and the final detection value.

2. The multi-range hydrogen sensor according to claim 1, characterized in that, Parameter differentiation settings include parameter settings that are incremental or hierarchical; The overlap ratio of the overlapping range is 5%-50%; the overlap ratio is the ratio of the overlap width of two adjacent detection intervals to the width of the narrower detection interval.

3. The multi-range hydrogen sensor according to claim 2, characterized in that, The number of sensing units is four, and the geometric coding groups of the four sensing units are as follows: First sensing unit: P is 200-300nm, H is 150-170nm, D is 40-42nm; Second sensing unit: P is 400-500nm, H is 170-190nm, D is 45-47nm; Third sensing unit: P is 600-700nm, H is 190-210nm, D is 50-52nm; Fourth sensing unit: P is 800-900nm, H is 210-230nm, and D is 55-57nm.

4. A decoding method based on the multi-range hydrogen sensor according to any one of claims 1 to 3, characterized in that, Includes the following steps: During testing, the baseline resistance of the i-th sensing unit in the initial sensing unit sequence is collected under a reference atmosphere. Under the atmosphere of the concentration to be measured, when the real-time resistance of the i-th sensing unit reaches the preset steady-state ratio, the response resistance at this time is recorded. And record the response time at this time. , where 1≤i≤n, and n is the total number of sensing units; According to the above and Calculate the response resistance parameter of the i-th sensing unit under the measured concentration atmosphere. ; Obtain the initial dataset for the i-th sensing unit; Based on the initial dataset of the i-th sensing unit, and After normalization, the normalized response resistance parameters of the i-th sensing unit under the measured concentration atmosphere are obtained. and normalized response time ; Based on the i-th sensing unit , Normalized response resistance parameter window Normalized response time window Calculate the matching degree A of the i-th sensing unit. i ; A i Sort the candidate sensing units in ascending order to obtain a sequence, and select A. i The smallest sensing unit is selected as the candidate decoding unit; Perform the first verification step on the candidate decoding unit. If the first verification passes, output the candidate concentration. The measured concentration is used as the actual concentration, and the detection range of the candidate decoding unit is output as the actual measurement range. If the first verification fails, the other adjacent detection unit corresponding to the overlapping range is set as the specific detection unit, and the second verification step is performed on the candidate decoding unit and the specific detection unit. If the second verification passes, output As the measured concentration, the detection range of the candidate decoding unit is output as the measured range; otherwise, the next sensing unit in the candidate sensing unit sequence is selected as the candidate decoding unit, and the first verification step is re-executed until the output result is obtained. The first verification step includes: Based on the target concentration-response resistance parameter mapping curve of the candidate decoding unit and the response resistance parameter of the candidate decoding unit, we obtain ; like If the detection range of the candidate decoding unit does not fall within the detection overlap range of the adjacent sensing unit, or is equal to the overlap boundary value, then the first verification passes; otherwise, it fails. The second verification step includes: Based on the position k of the specific detection unit in the initial sensing unit sequence, obtain the normalized response resistance parameter of the specific detection unit under the atmosphere of the concentration to be measured. and normalized response time ; Will Substituting the target concentration-normalized response resistance parameter mapping curve and the target concentration-normalized response time mapping curve of the specific detection unit within the overlapping range, the theoretical normalized response resistance parameter is obtained. and theoretical normalized response time ; according to and Calculate the overall trend deviation E of a specific detection unit k The allowable deviation threshold ε for verification of a specific detection unit k For comparison, if E k ≤ε k If yes, the second verification passes; otherwise, the second verification fails.

5. The decoding method for a multi-range hydrogen sensor according to claim 4, characterized in that: The initial dataset of the i-th sensing unit includes the following for the i-th sensing unit: geometric coding group, abnormal drift judgment threshold, pre-calibrated mapping curve, pre-calibrated response window, and response trend data of the overlapping range of adjacent sensing units. The pre-calibrated mapping curves include: target concentration-response resistance parameter mapping curve, target concentration-response time mapping curve, target concentration-normalized response resistance parameter mapping curve, and target concentration-normalized response time mapping curve. The pre-calibrated response window includes: a normalized response resistance parameter window and a normalized response time window; The overlap range response trend data of the adjacent sensing units includes: Target concentration-normalized response resistance parameter mapping curves of adjacent sensing units in the overlapping range; Target concentration-normalized response time mapping curves of adjacent sensing units in the overlapping range; Verification allowable deviation threshold for adjacent sensing units.

6. The decoding method for a multi-range hydrogen sensor according to claim 5, characterized in that: The calibration method for the target concentration-response resistance parameter mapping curve, target concentration-response time mapping curve, target concentration-normalized response resistance parameter mapping curve, and target concentration-normalized response time mapping curve of the i-th sensing unit is as follows: Define the detection range of the i-th sensing unit And select m concentration values ​​C within the detection interval. M , 1≤M≤m; Record the calibration baseline resistance of the i-th sensing unit under the reference atmosphere. And record the i-th sensing unit in C M Calibration response resistor under atmosphere and calibrated response time ; according to and Calculate the value of the i-th sensing unit in C. M Calibration response resistance parameters under different atmospheres The calculation formula is: ； Will and the corresponding C M By fitting the data, the target concentration-response resistance parameter mapping curve of the i-th sensing unit is obtained. ,in, S is the target concentration-response resistance parameter mapping function. i Let C be the calibration response resistance parameter of the i-th sensing unit, and C be a formal parameter representing the concentration, satisfying... ; Will After normalization, the value of the i-th sensing unit in C is obtained. M Normalized calibration response resistance parameters under different atmospheres The calculation formula is: ； Among them, S i,min For S i Minimum value, S i,max For S i Maximum value; Will and the corresponding C M By fitting the data, the target concentration-normalized response resistance parameter mapping curve of the i-th sensing unit is obtained. ,in, Let X be the target concentration-normalized response resistance parameter mapping function. i The normalized calibration response resistance parameter is set for the i-th sensing unit; Will and the corresponding C M By fitting the data, the target concentration-response time mapping curve of the i-th sensing unit is obtained. ,in, Let T be the target concentration-response time mapping function. i Let be the calibration response time of the i-th sensing unit; Will After normalization, the value of the i-th sensing unit in C is obtained. M Normalized calibration response time under different atmospheres The calculation formula is: ； Among them, T i,min For T i Minimum value, T i,max For T i Maximum value; Will and the corresponding C M By fitting the data, the target concentration-normalized response time mapping curve of the i-th sensing unit is obtained. ,in, Y is the target concentration-normalized response time mapping function. i The normalized calibration response time for the i-th sensing unit; The calibration method for the normalized response resistance parameter window and the normalized response time window of the i-th sensing unit is as follows: Select S i Within the range of values, the minimum calibrated response resistance parameter that meets the preset signal-to-noise ratio requirement. ,calculate The corresponding normalized calibrated response resistance parameter a i and according to exist Find the corresponding concentration C a According to C a exist Find the corresponding normalized calibration response time c. i ; Select The above refers to the calibration response resistance parameter corresponding to the differential slope decreasing to the preset slope. ,calculate The corresponding normalized calibration response resistance parameter b i and according to exist Find the corresponding concentration C b According to C b exist Find the corresponding normalized calibration response time d. i ; Obtain the normalized response resistance parameter window and normalized response time window ; The method for determining the verification allowable deviation threshold of the adjacent sensing units includes: Obtain the position j of the adjacent sensing unit in the initial sensing unit sequence, 1≤j≤n; Select one known concentration value C within the detection interval. L , 1≤L≤l; Record adjacent sensing units in C L Response resistance under atmosphere and calibrated response time ; according to and Calculate the adjacent sensing units in C L Response resistance parameters under different atmospheres The calculation formula is: ； Will Normalization is performed to obtain the values ​​of adjacent sensing units in C. L Normalized response resistance parameters under different atmospheres The calculation formula is: ； Will Normalization is performed to obtain the values ​​of adjacent sensing units in C. L Normalized response time under different atmospheres The calculation formula is: ； according to , Adjacent sensing units in C L Theoretical normalized response resistance parameters under different atmospheres and adjacent sensing units in C L Theoretical normalized response time under atmosphere Calculate the comprehensive residual sequence The calculation formula is: ； in, Here, η is the weighting coefficient for the normalized response resistance parameter, and η is the weighting coefficient for the normalized response time. ; Will Sort by numerical value and use a preset percentage quantile as the verification allowable deviation threshold ε for adjacent sensing units. j ; The formation of different response characteristics includes forming different target concentration-normalized response resistance parameter mapping curves and target concentration-normalized response time mapping curves.

7. The decoding method for a multi-range hydrogen sensor according to claim 6, characterized in that, The Calculated using the following formula: ； The Calculated using the following formula: ； The Calculated using the following formula: ； The A i Calculated using the following formula: ； In the formula, For window distance function, , ; when Located in [a i ,b i [Inner time,] ;when hour, ;when hour, ; when Located in [c i ,d i [Internal Time] ;when hour, ;when hour, ; α and β are both weighting coefficients, and α + β = 1; The overall trend deviation E k Calculated using the following formula: ； In the formula, γ+δ=1, where γ is the weighting coefficient of the response resistance parameter and δ is the weighting coefficient of the response time.

8. The decoding method for a multi-range hydrogen sensor according to claim 4, characterized in that, When the baseline resistance of any sensing unit drifts beyond a preset drift threshold, an alarm and a device replacement prompt will be output.

9. A method for preparing a multi-range hydrogen sensor as described in any one of claims 1 to 3, characterized in that, Includes the following steps: A common conductive layer and an Al film are sequentially deposited on the substrate surface; According to the preset P, cover and protect the Al film, expose the preset sensing unit forming areas on the Al film one by one, selectively anodize the exposed sensing unit forming areas to form AAO template areas, and cover and protect the already formed AAO template areas before exposing the next sensing unit forming area to obtain the first-processed AAO template area. Based on the preset H, the barrier layer of AAO template regions with different P is thinned to obtain the secondary processed AAO template regions. According to the preset D, the AAO template area with H is subjected to hole opening and secondary hole expansion processing to obtain the AAO template area with three processing steps. Copper nanowires were electrodeposited in the open area of ​​the AAO template region after three treatments, and the height of the nanowires in different regions was controlled by adjusting the electrodeposition time so that the final height was the same as the preset H. After removing the AAO template, copper nanowires were subjected to an oxidation heat treatment to obtain a CuO nanowire array. Independent electrodes were fabricated and then cut, bonded, and packaged to obtain the final multi-range hydrogen sensor.

10. The preparation method according to claim 9, characterized in that: Before sequentially depositing the common conductive layer and Al film on the substrate surface, the substrate needs to be pretreated. A partitioned photolithography mask process is used to selectively anodize the exposed sensor unit formation area; The selective anodizing process uses a phosphoric acid electrolyte, with an anodizing voltage of 45-200V and an anodizing time of 20-90min. The barrier layer thinning adopts a stepped pressure-reducing anodizing process, and the opening and secondary pore expansion adopt a 5% phosphoric acid solution with a pore expansion time of 10-30 min. The thickness of the common conductive layer is 50-100 nm, and the thickness of the Al film is 3-4 μm; The oxidation heat treatment temperature is 300-350℃, and the holding time is 2-4h.

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