CN1945303A - Array filmsensor for simultaneously detecting Cu2+, Pb2+, Cd2+ and its preparing method - Google Patents
Array filmsensor for simultaneously detecting Cu2+, Pb2+, Cd2+ and its preparing method Download PDFInfo
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- CN1945303A CN1945303A CN 200610017279 CN200610017279A CN1945303A CN 1945303 A CN1945303 A CN 1945303A CN 200610017279 CN200610017279 CN 200610017279 CN 200610017279 A CN200610017279 A CN 200610017279A CN 1945303 A CN1945303 A CN 1945303A
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Abstract
The array film sensor for simultaneously detecting Cu2+, Pb2+ and Cd2+ ions includes one P-type or N-type Si chip as substrate, one SiO2 layer and three kinds of film sensitive separately to Cu2+, Pb2+ and Cd2+ ions successively on the substrate. It is prepared through one laser pulse depositing process to prepare these three kinds of film on the surface of SiO2. It is selective on Cu2+, Pb2+ and Cd2+ ions in solution, and may be used in detecting the contents of Cu2+, Pb2+ and Cd2+ ions. The present invention may be used for the simultaneous qualitative and quantitative detection of Cu2+, Pb2+ and Cd2+ in river and lake water, blood, body fluid, industrial effluent, Chinese medicine, vegetable, fruit, tea, etc.
Description
Technical field
The present invention relates to a kind of sensor and preparation method who is used for detecting simultaneously several heavy metal species, relate in particular to and be used for detecting simultaneously Cu
2+, Pb
2+, Cd
2+Array thin film sensor and preparation method thereof.
Background technology
Heavy metal ion is (as Zn
2+, Pb
2+, Cd
2+, Cu
2+, Cr
6+, Mn
5+, As
3+, Fe
3+, Hg
2+) can produce harmful even fatal influence to human body, so the detection by quantitative of heavy metal has very important meaning at aspects such as medicine, food, clinical and environmental monitorings.Present detection method mainly contains atomic absorption spectrophotometry and mass spectroscopy etc., but adopt the equipment of these methods huge, and expensive, need complicated pretreatment, measuring period is long and need skilled operating personnel, and this brings many inconveniences in actual applications.
Summary of the invention
The object of the present invention is to provide a kind of Cu that is used for detecting simultaneously
2+, Pb
2+, Cd
2+Array thin film sensor and preparation method thereof, can be to Cu
2+, Pb
2+, Cd
2+Carry out qualitative and detection by quantitative simultaneously.
In order to achieve the above object, the technical solution used in the present invention is as follows:
A kind ofly be used for detecting simultaneously Cu
2+, Pb
2+, Cd
2+The array thin film sensor, do substrate with p type or n type Si sheet, be SiO on substrate
2Layer, SiO
2Above the layer is to Cu
2+, Pb
2+, Cd
2+Three kinds of responsive films;
A kind ofly be used for detecting simultaneously Cu
2+, Pb
2+, Cd
2+The preparation method of array thin film sensor, it is made up of the following step:
(1) preparation of thin film sensor substrate and oxide layer
Select p type or n type＜100 for use〉monocrystalline silicon piece is as the substrate of thin film sensor, and described silicon chip is put into high temperature furnace and is carried out thermal oxide after polished and cleaned, makes the silicon chip front layer thickness of growing in dry oxygen be about the SiO of 30nm
2Film removes the oxide layer at the silicon chip back side with ion etching method, starches the Ohmic contact of making an annular with silver then and draws lead, and except annular position, remainder is all used epoxy sealing, promptly makes needed thin film sensor substrate;
(2) preparation of sensitive material
Select high-purity compound CuS, Ag for use
2S, CuI
2, its mol ratio is 55～65: 20～30: 10～20, fully behind the mixed grinding, under 12Mpa pressure, make little rectangular parallelepiped, and be put in the quartzy bottle, under the condition of nitrogen gas of drying, be heated to 540 ℃, kept 4 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm: thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 540 ℃, kept 4 hours; Naturally the preparation of Cu sensitive material has promptly been finished in annealing then, just makes the Cu target of pulsed laser deposition technique;
Select high-purity compound PbS, Ag for use
2S, PbI
2, its mol ratio is 50～60: 20～30: 10～20, fully behind the mixed grinding, under 8Mpa pressure, make little rectangular parallelepiped, and be put in the quartzy bottle, under the condition of nitrogen gas of drying, be heated to 420 ℃, kept 5 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm: thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 420 ℃, kept 5 hours; Naturally the preparation of Pb sensitive material has promptly been finished in annealing then, just makes the Pb target of pulsed laser deposition technique;
Select high-purity compound CdS, Ag for use
2S and CdI
2, its mol ratio is 45～55: 20～30: 15～25, fully behind the mixed grinding, under 16Mpa pressure, make little rectangular parallelepiped, and be put in the quartzy bottle, under the condition of nitrogen gas of drying, be heated to 450 ℃, kept 4 hours; Naturally annealing is then ground little rectangular parallelepiped brokenly more again, and make diameter/be 3cm: thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 450 ℃, kept 4 hours; Naturally the preparation of Cd sensitive material has promptly been finished in annealing then, just makes the Cd target of pulsed laser deposition technique;
(3) preparation of film
Adopt pulsed laser deposition technique on sensor base, to prepare sensitive thin film, use pulsed laser deposition technique, at SiO
2Preparation is to Cu
2+, Pb
2+, Cd
2+Responsive film is at SiO
2Form three film zones on the layer, pulsed laser deposition equipment mainly is made up of laser generator and vacuum chamber; Above-mentioned film preparation procedure parameter is:
| The deposition process parameter | The Cu experiment value | The Pb experiment value | The Cd experiment value |
| Energy density wavelength pulse width repetition rate sedimentation time pressure base reservoir temperature target material | 0.2J/cm 2 248nm 30ns 4Hz 50min 0.3mbar N 2 373K Cu-Ag-I-S | 0.2J/cm 2 248nm 30ns 5Hz 40min 0.25mbar N 2 373K Pb-Ag-I-S | 0.2J/cm 2 248nm 30ns 6Hz 60min 0.4mbar N 2 373K Cd-Ag-I-S |
The advantage that the present invention has is: can detect Cu simultaneously
2+, Pb
2+, Cd
2+Three heavy metal species ions, detection means is little, and sample solution is few, measures fast, and is easy to use, measures accurately, and interfering ion is few.This thin film sensor can be to Cu in fields such as rivers,lakes and seas, biomedical sector such as blood, body fluid etc., industrial waste water, Chinese medicine, vegetables, fruit, tealeaves
2+, Pb
2+, Cd
2+Carry out qualitative and detection by quantitative.
Description of drawings
The invention will be further described below in conjunction with the drawings and specific embodiments.
Fig. 1 is a plan structure synoptic diagram of the present invention;
Fig. 2 is the A-A cut-open view of Fig. 1;
Fig. 3 is that pulsed laser deposition technique prepares the thin-film process schematic diagram;
Fig. 4 is Cu
2+The canonical plotting of thin film sensor;
Fig. 5 is Pb
2+The canonical plotting of thin film sensor;
Fig. 6 is Cd
2+The canonical plotting of thin film sensor;
Embodiment
Now in conjunction with the accompanying drawings and embodiment, it is as follows that the present invention is further illustrated:
Be used for detecting simultaneously Cu from Fig. 2 and the visible the present invention of Fig. 1
2+, Pb
2+, Cd
2+The array thin film sensor, be to select for use p type or n type Si sheet to do substrate, be SiO above the substrate at this
2Layer, SiO
2There are three kinds respectively to Cu above the layer
2+, Pb
2+, Cd
2+Responsive film.
The present invention is used for detecting simultaneously Cu
2+, Pb
2+, Cd
2+The preparation of array thin film sensor, form by following steps:
(1) preparation of thin film sensor substrate and oxide layer
Select p type or n type＜100 for use〉monocrystalline silicon piece is as substrate.Silicon chip is put into high temperature furnace and is carried out thermal oxide after polished and cleaned, makes the silicon chip front layer thickness of growing in dry oxygen be about the SiO of 30nm
2Film, with ion etching method the oxide layer at the silicon chip back side is removed, starch the Ohmic contact of making an annular with silver then and draw lead, except annular position stays, remainder is all used epoxy sealing, promptly make described thin film sensor substrate, excitation source adopts the front or the back side all can;
(2) preparation of sensitive material
Select high-purity compound CuS, Ag for use
2S, CuI
2, its mol ratio 55: 20: 10 fully behind the mixed grinding, under 12Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 540 ℃, keeps 4 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the thin rounded flakes of 2mm; Be placed in the vitreosil bottle, be heated to 540 ℃, kept 4 hours, the preparation of Cu sensitive material has promptly been finished in annealing naturally, has just obtained the Cu target of pulsed laser deposition technique;
Select high-purity compound PbS, Ag for use
2S, PbI
2, its mol ratio 50: 20: 10 fully behind the mixed grinding, under 8Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 420 ℃, keeps 5 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the thin rounded flakes of 2mm; Be placed in the vitreosil bottle, be heated to 420 ℃, kept 5 hours, the preparation of Pb sensitive material has promptly been finished in annealing naturally, just makes the Pb target of pulsed laser deposition technique;
Select high-purity compound CdS, Ag for use
2S, CdI
2, its mol ratio 45: 20: 15 fully behind the mixed grinding, under 16Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 450 ℃, keeps 4 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the circle sheet of 2mm; Be placed in the vitreosil bottle, be heated to 450 ℃, kept 4 hours, the preparation of Cd sensitive material has promptly been finished in annealing naturally, just makes the Cd target of pulsed laser deposition technique;
(3) preparation of film
Adopt pulsed laser deposition technique, prepare sensitive thin film on sensor base, pulsed laser deposition equipment mainly is made up of laser generator and vacuum chamber; Figure 3 shows that pulsed laser deposition technique prepares the film schematic diagram, the laser beam scioptics shine on the sensitive material target material surface after focusing on, and the reflection back forms plasma slab at target material surface, and the sensitive material that excites is evaporated in the substrate, forms sensitive thin film.Preparation process is divided into three times, prepares a kind of film each time, and depositional area accounts for 1/3rd of whole circular silicon chip, has deposited the film of three kinds of homalographics at last on a circular silicon chip.In order to guarantee combining closely of film and metal level, substrate is warmed up to 100 ℃, and preheating 20 minutes finishes the back in deposition and kept 10 minutes, cooling naturally in vacuum chamber then.
(1) preparation of thin film sensor substrate and oxide layer
Select p type or n type＜100 for use〉monocrystalline silicon piece is as substrate.Silicon chip is put into high temperature furnace and is carried out thermal oxide after polished and cleaned, makes the silicon chip front layer thickness of growing in dry oxygen be about the SiO of 30nm
2Film, with ion etching method the oxide layer at the silicon chip back side is removed, starch the Ohmic contact of making an annular with silver then and draw lead, except annular position stays, remainder is all used epoxy sealing, promptly make described thin film sensor substrate, excitation source adopts the front or the back side all can;
(2) preparation of sensitive material
Select high-purity compound CuS, Ag for use
2S, CuI
2, its mol ratio 60: 25: 15 fully behind the mixed grinding, under 12Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 540 ℃, keeps 4 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the thin rounded flakes of 2mm; Place it in the vitreosil bottle, be heated to 540 ℃, kept 4 hours, the preparation of Cu sensitive material has promptly been finished in annealing naturally, has just obtained the Cu target of pulsed laser deposition technique;
Select high-purity compound PbS, Ag for use
2S, PbI
2, its mol ratio 55: 25: 15 fully behind the mixed grinding, under 8Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 420 ℃, keeps 5 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the thin rounded flakes of 2mm; Place it in the vitreosil bottle, be heated to 420 ℃, kept 5 hours, the preparation of Pb sensitive material has promptly been finished in annealing naturally, just makes the Pb target of pulsed laser deposition technique;
Select high-purity compound CdS: Ag for use
2S: CdI
2Mol ratio 50: 25: 20 fully behind the mixed grinding, under 16Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 450 ℃, keeps 4 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 450 ℃, kept 4 hours, annealing has promptly been finished the preparation of Cd sensitive material, just the Cd target of pulsed laser deposition technique naturally;
(3) preparation of film
Adopt pulsed laser deposition technique, prepare sensitive thin film on sensor base, pulsed laser deposition equipment mainly is made up of laser generator and vacuum chamber; Figure 3 shows that pulsed laser deposition technique prepares the film schematic diagram, the laser beam scioptics shine on the sensitive material target material surface after focusing on, and the reflection back forms plasma slab at target material surface, and the sensitive material that excites is evaporated in the substrate, forms sensitive thin film.Preparation process is divided into three times, prepares a kind of film each time, and depositional area accounts for 1/3rd of whole circular silicon chip, has deposited the film of three kinds of homalographics at last on a circular silicon chip.In order to guarantee combining closely of film and metal level, substrate is warmed up to 100 ℃, and preheating 20 minutes is at the deposition knot
(1) preparation of thin film sensor substrate and oxide layer
Select p type or n type＜100 for use〉monocrystalline silicon piece is as substrate.Silicon chip is put into high temperature furnace and is carried out thermal oxide after polished and cleaned, makes the silicon chip front layer thickness of growing in dry oxygen be about the SiO of 30nm
2Film, with ion etching method the oxide layer at the silicon chip back side is removed, starch the Ohmic contact of making an annular with silver then and draw lead, except annular position stays, remainder is all used epoxy sealing, promptly make described thin film sensor substrate, excitation source adopts the front or the back side all can;
(2) preparation of sensitive material
Select high-purity compound CuS, Ag for use
2S, CuI
2, its mol ratio 65: 30: 20 fully behind the mixed grinding, under 12Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 540 ℃, keeps 4 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the thin rounded flakes of 2mm; Place it in the vitreosil bottle, be heated to 540 ℃, kept 4 hours, the preparation of Cu sensitive material has promptly been finished in annealing naturally, has just obtained the Cu target of pulsed laser deposition technique;
Select high-purity compound PbS, Ag for use
2S, PbI
2, its mol ratio 60: 30: 20 fully behind the mixed grinding, under 8Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 420 ℃, keeps 5 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 420 ℃, kept 5 hours, the preparation of Pb sensitive material has promptly been finished in annealing naturally, just makes the Pb target of pulsed laser deposition technique;
Select high-purity compound CdS: Ag for use
2S: CdI
2Mol ratio 55: 30: 25 fully behind the mixed grinding, under 16Mpa pressure, is made little rectangular parallelepiped, is put in the quartzy bottle, under the condition of nitrogen gas of drying, is heated to 450 ℃, keeps 4 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm, thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 450 ℃, kept 4 hours, annealing has promptly been finished the preparation of Cd sensitive material, just the Cd target of pulsed laser deposition technique naturally;
(3) preparation of film
Adopt pulsed laser deposition technique, prepare sensitive thin film on sensor base, pulsed laser deposition equipment mainly is made up of laser generator and vacuum chamber; Figure 3 shows that pulsed laser deposition technique prepares the film schematic diagram, the laser beam scioptics shine on the sensitive material target material surface after focusing on, and the reflection back forms plasma slab at target material surface, and the sensitive material that excites is evaporated in the substrate, forms sensitive thin film.Preparation process is divided into three times, prepares a kind of film each time, and depositional area accounts for 1/3rd of whole circular silicon chip, has deposited the film of three kinds of homalographics at last on a circular silicon chip.In order to guarantee combining closely of film and metal level, substrate is warmed up to 100 ℃, and preheating 20 minutes finishes the back in deposition and kept 10 minutes, cooling naturally in vacuum chamber then.
Following table prepares the parameter of thin-film process for embodiment 1～3 pulsed laser deposition technique:
Table 1 pulsed laser deposition technique prepares the thin-film process parameter
| The deposition process parameter | The Cu experiment value | The Pb experiment value | The Cd experiment value |
| Energy density wavelength pulse width repetition rate sedimentation time pressure base reservoir temperature target material | 0.2J/cm 2 248nm 30ns 4Hz 50min 0.3mbar N 2 373K Cu-Ag-I-S | 0.2J/cm 2 248nm 30ns 5Hz 40min 0.25mbar N 2 373K Pb-Ag-I-S | 0.2J/cm 2 248nm 30ns 6Hz 60min 0.4mbar N 2 373K Cd-Ag-I-S |
The principle of work of sensor:
The change of semiconductor Dc bias can cause the variation of inner photogenerated current, and in the constant thin film sensor of fixed-bias transistor circuit, film is to the Cu in the electrolyte solution
2+, Pb
2+, Cd
2+Selectivity be the determinative that electric current causes variation in the loop, different concentration can cause the change of electric current, changes by the electric current of measuring in the external circuit, just can reflect the Cu in the solution
2+, Pb
2+, Cd
2+Concentration.
Excitation source adopts laser diode, can front or back side illuminaton; Contrast electrode is selected platinum electrode or Ag/AgCl for use; Ohmic contact is drawn lead and is connect direct supply, and direct supply has been the effect of bias voltage; Measure solution and can cause the variation of sensitive membrane current potential, thereby cause that the electric current in the circuit loop changes, just can measure contained Cu in the solution by the photocurrent variations that measures
2+, Pb
2+, Cd
2+Concentration.
The characteristic of sensor:
Thin film sensor is to Cu
2+, Pb
2+, Cd
2+Optionally typical curve such as Fig. 3, Fig. 4 and shown in Figure 5.Detect lower limit and be respectively 1 * 10
-6Mol/L, 2 * 10
-7Mol/L and 1 * 10
-7Mol/L.The response time of three kinds of thin film sensors omits hurry up when concentration is high relatively all less than 1min.And when measuring high concentration Cu
2+, Pb
2+, Cd
2+Behind the solution, when measuring low concentration again, do not find significant concentration hesitation phenomenon.
Claims (2)
1, a kind ofly is used for detecting simultaneously Cu
2+, Pb
2+, Cd
2+The array thin film sensor, do substrate with p type or n type Si sheet, be SiO in substrate
2Layer, SiO
2Above the layer is to Cu
2+, pb
2+, Cd
2+Three kinds of responsive films.
2, as claimed in claim 1ly be used for detecting simultaneously Cu
2+, Pb
2+, Cd
2+The preparation method of array thin film sensor, this method is made up of following steps:
(1) preparation of thin film sensor substrate and oxide layer
Select the described type of p type or n＜100〉monocrystalline silicon piece substrates as thin film sensor for use, described silicon chip is put into high temperature furnace and is carried out thermal oxide after polished and cleaned, makes the silicon chip front layer thickness of growing in dry oxygen be about the SiO of 30nm
2Film removes the oxide layer at the silicon chip back side with ion etching method, starches the Ohmic contact of making an annular with silver then and draws lead, and except annular position, remainder is all used epoxy sealing, promptly makes needed thin film sensor substrate;
(2) preparation of sensitive material
Select high-purity compound CuS, Ag for use
2S, CuI
2, its mol ratio is 55～65: 20～30: 10～20, fully behind the mixed grinding, under 12Mpa pressure, make little rectangular parallelepiped, and be put in the quartzy bottle, under the condition of nitrogen gas of drying, be heated to 540 ℃, kept 4 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm: thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 540 ℃, kept 4 hours; Naturally annealing has promptly been finished the preparation of Cu sensitive material, just the Cu target of pulsed laser deposition technique then;
Select high-purity compound PbS, Ag for use
2S, PbI
2, its mol ratio is 50～60: 20～30: 10～20, fully behind the mixed grinding, under 8Mpa pressure, make little rectangular parallelepiped, and be put in the quartzy bottle, under the condition of nitrogen gas of drying, be heated to 420 ℃, kept 5 hours; Naturally annealing then, broken little rectangular parallelepiped grinding again again, making diameter is 3cm: thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 420 ℃, kept 5 hours; Naturally the preparation of Pb sensitive material has promptly been finished in annealing then, just makes the Pb target of pulsed laser deposition technique;
Select high-purity compound CdS, Ag for use
2S and CdI
2, its mol ratio is 45～55: 20～30: 15～25, fully behind the mixed grinding, under 16Mpa pressure, make little rectangular parallelepiped, and be put in the quartzy bottle, under the condition of nitrogen gas of drying, be heated to 450 ℃, kept 4 hours; Naturally annealing is then ground little rectangular parallelepiped brokenly more again, and make diameter/be 3cm: thickness is the circle sheet of 2mm; Place it in the vitreosil bottle, be heated to 450 ℃, kept 4 hours; Naturally the preparation of Cd sensitive material has promptly been finished in annealing then, just makes the Cd target of pulsed laser deposition technique;
(3) preparation of film
Adopt pulsed laser deposition technique on sensor base, to prepare sensitive thin film, use pulsed laser deposition technique, at SiO
2Prepare Cu respectively on the layer
2+, Pb
2+, Cd
2+Responsive film is at SiO
2Form three film zones on the layer, pulsed laser deposition equipment mainly is made up of laser generator and vacuum chamber; Above-mentioned preparation thin-film process parameter is:
Deposition process parameters C u experiment value Pb experiment value Cd experiment value
Energy density 0.2J/cm
220.2J/cm
20.2J/cm
2
Wavelength 248nm 248nm 248nm
Pulse width 30ns 30ns 30ns
Repetition frequency 4Hz 5Hz 6Hz
Sedimentation time 50min 40min 60min
Pressure 0.3mbar N
20.25mbar N
20.4mbar N
2
Base reservoir temperature 373K 373K 373K
Target material Cu-Ag-I-S Pb-Ag-I-S Cd-Ag-I-S.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610017279XA CN100434910C (en) | 2006-10-24 | 2006-10-24 | Array filmsensor for simultaneously detecting Cu2+, Pb2+, Cd2+ and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610017279XA CN100434910C (en) | 2006-10-24 | 2006-10-24 | Array filmsensor for simultaneously detecting Cu2+, Pb2+, Cd2+ and its preparing method |
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| Publication Number | Publication Date |
|---|---|
| CN1945303A true CN1945303A (en) | 2007-04-11 |
| CN100434910C CN100434910C (en) | 2008-11-19 |
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ID=38044798
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102507698A (en) * | 2011-09-23 | 2012-06-20 | 广东省微生物研究所 | Novel sensor for synchronously detecting copper ions and lead ions |
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| WO1999024825A1 (en) * | 1997-11-06 | 1999-05-20 | Forschungszentrum Jülich GmbH | Production of the chalcogenide glass layer of a heavy metal electrode by means of laser ablation |
| JPH11337514A (en) * | 1998-05-26 | 1999-12-10 | Omron Corp | Biosensor |
| JP3306506B2 (en) * | 1999-08-23 | 2002-07-24 | 独立行政法人産業技術総合研究所 | Ion sensor using acyclic peptide |
| CN1117983C (en) * | 2000-01-14 | 2003-08-13 | 浙江大学 | Multiple light source addressed potential sensor and parallelly processing gas image test set |
| JP3816296B2 (en) * | 2000-04-14 | 2006-08-30 | 独立行政法人科学技術振興機構 | Semiconductor depletion layer capacitance measuring method and apparatus |
| JP4456303B2 (en) * | 2000-09-06 | 2010-04-28 | 株式会社堀場製作所 | pH sensor |
| CN1235044C (en) * | 2003-12-14 | 2006-01-04 | 浙江大学 | Film optical addressing electric potential sensor used for detecting Hg2+ and preparation method thereof |
| CN1242259C (en) * | 2003-12-14 | 2006-02-15 | 浙江大学 | Film optical addressing electric potential sensor used for detecting Fe3+ and preparation method thereof |
| CN2660528Y (en) * | 2003-12-21 | 2004-12-01 | 浙江大学 | Thin film optical addressing potential sensor for detecting heavy metal ions |
| CN1558216A (en) * | 2004-01-16 | 2004-12-29 | 华东理工大学 | Spectrophotometry for measuring residual phosphorus content in benzoxazole class polyfibre or film |
| DE102004044299A1 (en) * | 2004-09-10 | 2006-03-30 | Forschungszentrum Jülich GmbH | Apparatus and method for detecting charged macromolecules |
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