CN102944322B - Heterojunction pure resistance-diode composite thermometer - Google Patents
Heterojunction pure resistance-diode composite thermometer Download PDFInfo
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- CN102944322B CN102944322B CN201210485015.2A CN201210485015A CN102944322B CN 102944322 B CN102944322 B CN 102944322B CN 201210485015 A CN201210485015 A CN 201210485015A CN 102944322 B CN102944322 B CN 102944322B
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Abstract
The invention relates to a heterojunction pure resistance-diode composite thermometer which is provided with a Co/CoO-ZnO/Ag heterojunction. In the heterojunction, Co is a bottom electrode, Ag is a top electrode, and CoO-ZnO is a composite insulating layer. When in measurement, the Ag top electrode and the Co bottom electrode of the heterojunction are connected with an external circuit measuring meter. When silver has positive voltage and cobalt has negative voltage, the heterojunction is low in resistance, and high temperature is measured by an R-T curve corresponding to conductivity of metal in low resistance. When the silver has negative voltage and the cobalt has positive voltage, the heterojunction is high in resistance, low temperature is measured by an R-T curve corresponding to conductivity of a semiconductor in high resistance, and the temperature measuring range is 5K-300K. The thermometer is wide in temperature measuring range, can ensure the same measuring precision within a large range, is short in temperature response time and quite sensitive, and can be used for measuring the temperature of a micron-sized object.
Description
Technical field
The present invention relates to a kind of heterojunction pure resistance-diode combined temp meter, belong to semiconductor materials and devices field.
Background technology
The measurable temperature range of existing thermometer is conventionally narrow, when measuring in the situation of wide region temperature, must prepare the temperature survey of several thermometers for different range.Therefore prepare a kind of thermometer that can accurately measure high and low temperature simultaneously and will bring great convenience to temperature survey under various complex situations.
CN200510011171.5(CN1632484A) provide a kind of temperature sensor based on disordered multi-wall nano carbon tube-heterojunction, comprise insulation and thermal insulation pipe, be filled in the multi-walled carbon nano-tubes powder pillar in insulation and thermal insulation pipe, be arranged on multi-walled carbon nano-tubes powder pillar one end and form the metal temperature probe of carbon nano-tube-metal hetero-junction and seal the conducting metal piece that is pressed in the carbon nanotube powder post other end with carbon nanotube powder post close contact.During work, first electrode is connected with external circuit measurement instrument, then metal temperature probe is contacted with testee, like this, due to the existence of carbon nano-tube-metal hetero-junction, in circuit, can produce temperature variant thermic electric current, can measure temperature range wide, in on a large scale, all can guarantee same measuring accuracy, fast to the response time of temperature.
Research is found, in metal/insulator/metal (MIM) structure, can cause resistive phenomenon because redox reaction causes obvious electricity.But this theoretical research not yet has the report of the product development that is applied to thermometer.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of heterojunction pure resistance-diode combined temp meter based on Co/CoO-ZnO/Ag heterojunction, can be used for micrometer range temperature survey.The present invention also provides the preparation method of described combined temp meter.
Term explanation:
Electricity is sent a telegraph resistance: the phenomenon that the sample that additional electric pulse causes is changed back and forth between several stable ohmic states.
Bipolar resistive random: the electric resistance changing of sample depends on the polarity of added electric signal, for example: while adding forward voltage, sample becomes low resistance state from high-impedance state, becomes high-impedance state while adding reverse voltage from low resistance state.
HRS: high-impedance state, now sample is in high resistance state, shows semiconductor conductive characteristic, and corresponding R-T curve can be used to measure low temperature.
LRS: low resistance state, now sample is in low resistance state, shows metallic conduction characteristic, and corresponding R-T curve can be used to measure high temperature.
Vset: sample required external voltage when HRS becomes LRS.
Vreset: sample required external voltage when LRS becomes HRS.
Micrometer range temperature survey, refers to the temperature survey of 5K ~ 300K scope, and the size of measuring object may diminish to micron order.
Technical scheme of the present invention is as follows:
Heterojunction pure resistance-diode combined temp meter, comprises and uses Co/CoO-ZnO/Ag heterojunction, in this heterojunction, Co is bottom electrode, and Ag is top electrode, and CoO-ZnO is composite insulation layer.
In CoO-ZnO composite insulation layer, there is oxygen room (v) in ZnO layer, ZnO
1-vfor N-shaped semiconductor, CoO
1-xfor p-type semiconductor, both form p-n junction, show diode conduction characteristic.
Because heterojunction is very sensitive for thermotonus, can reach for micrometric objects and have temperature sense.Therefore heterojunction pure resistance-diode combined temp meter of the present invention can be used for the temperature survey of micrometer range object.
Under the alive effect outside of this series heterojunction, produce stable bipolar resistive random effect, selected bottom electrode Co ground connection in measuring process.When top electrode Ag adds certain positive voltage, heterojunction can become low resistance state from high-impedance state, and voltage is now called Vset; When top electrode Ag adds certain negative voltage, can become high-impedance state from low resistance state, voltage is now called Vreset.When heterojunction is in high-impedance state, the rising of its electrical resistance temperature and reducing, show semiconductor conductive characteristic, and the amplitude of variation of low-temperature space electrical resistance temperature is larger, therefore can utilize the high-impedance state Measurement accuracy low temperature of heterojunction.When heterojunction is in low resistance state, the rising of its electrical resistance temperature and increasing, shows metallic conduction characteristic, therefore can utilize the low resistance state of heterojunction to measure high temperature.Like this, owing to there is electricity under heterojunction alive effect outside, cause resistive, in circuit, can produce temperature variant electric current.
When measuring, the Ag of heterojunction, Co upper/lower electrode and external circuit measurement instrument are connected, in external circuit, be provided with two gears, respectively corresponding two reverse electrical source; When voltage silver just, cobalt when negative heterojunction in low resistance state, R-T curved measurement high temperature corresponding to metallic conduction characteristic while utilizing low resistance state; When voltage is that silver is negative, cobalt timing heterojunction is in high configuration; R-T curved measurement low temperature corresponding to semiconductor conductive characteristic while utilizing high resistance state, thus realize a thermometer and can measure the temperature range of 5K-300K.
Thermometer of the present invention, when measuring temperature within the scope of 5K-70K, utilizes high resistance state to measure temperature, and wherein the corresponding relation of resistance and temperature is: lnR=6.59+2.24*T
-1/4.
Thermometer of the present invention, when measuring temperature within the scope of 70K-300K, utilizes low resistance state to measure temperature, and wherein the corresponding relation of resistance and temperature is: R=51.35+0.068T.
The present invention is simple to operate, low in energy consumption, under the impressed voltage of ± 1V stimulates, can realize two kinds of resistance states, mutual conversion while being temperature survey between two gears, can accurately measure the low temperature that is low to moderate 5K, and measuring accuracy is high, preparation method is simple, has very wide application prospect.
The inventor is through long-term experimental study, the CoO layer forming between ZnO insulation course and bottom electrode Co metal in the middle of finding is sent a telegraph resistance phenomenon to the electricity of this heterojunction and is played conclusive effect, and successfully prepares the micron thermometer based on heterojunction Co/CoO-ZnO/Ag by the partial pressure of oxygen in sputtering power, sputtering time and sputter procedure in accurate control heterojunction preparation process.
According to the present invention, the preparation method of heterojunction Co/CoO-ZnO/Ag, utilizes magnetically controlled sputter method at Grown upper/lower electrode and middle ZnO insulation course described in thermometer, and process conditions and step are as follows:
Sputtering chamber vacuum is evacuated to 7.5 × 10
-5pa, take purity as more than 99.95% ZnO pottery and the more than 99.99% Co metal of purity and the more than 99.99% Ag metal of purity as target, ZnO is placed in to radio frequency target, Co and Ag are placed in respectively direct current target.Using purity as more than 99.99% high-purity Ar gas is as sputtering atmosphere, Ar gas enters sputtering chamber through gas meter.The sputtering power of Co is 5W, and sputtering pressure is 0.58Pa.The sputtering power of ZnO is 15W, and sputtering pressure is 0.65Pa.The sputtering power of Ag is 5W, and sputtering pressure is 0.55Pa.
Above substrate, place ground floor stainless steel mask, deposit respectively 1 ~ 2nm Cr, 25 ~ 35nmAg, 8～12nm Co, wherein Cr is as cushion, and Ag is electrode of metal, and Co is as the bottom electrode of heterojunction.Then replace with second layer stainless steel mask, the ZnO layer of sputtering sedimentation 8～12nm, the growth atmosphere of ZnO is Ar gas and O
2the combination gas of gas, wherein oxygen volume ratio is 5 ‰.Oxonium ion oxidation in the oxidized zinc of cobalt at ZnO and Co interface place forms CoO layer, and CoO layer is not Direct precipitation layer.Then replace with the 3rd layer of stainless steel mask, sputter 55 ~ 60nmAg is as electrode of metal.
Under the Co/CoO-ZnO/Ag heterojunction alive effect outside that utilizes magnetically controlled sputter method to grow, there is electricity and cause resistive, realize the mutual conversion between this heterojunction metallic conduction and two kinds of conduction states of semiconductor conduction.R-T curved measurement high temperature corresponding to metallic conduction characteristic while utilizing low resistance state, R-T curved measurement low temperature corresponding to semiconductor conductive characteristic while utilizing high resistance state, thus realize a thermometer and can measure the temperature range of 5K-300K
The heterojunction using in the present invention, as Co/CoO-ZnO/Ag heterojunction, there is a large amount of oxygen rooms in middle ZnO layer, and there is displacement in oxygen room, make the CoO in CoO-ZnO composite insulation layer under the effect of extra electric field
1-xlayer generation metal-insulator phase transition, realizes pure resistance and diode transforms mutually, thereby causes that the electricity of this heterojunction causes resistive phenomenon.When moving to Co electrode under the effect at extra electric field of the oxygen room of positively charged, CoO
1-xlayer changes metal Co into, and Co/CoO-ZnO/Ag is in low resistance state, and now heterojunction shows metallic conduction characteristic, the rising of electrical resistance temperature and linear increasing utilizes R-T curve now can measure very easily high temperature.When moving toward ZnO/Ag electrode under the effect of oxygen room at extra electric field, CoO
1-xlayer becomes the more CoO of insulation, even Co
1-xo p-type semiconductor, with N-shaped ZnO
1-vsemiconductor forms P-N knot, thereby shows semiconductor conductive characteristic, the now rising of the electrical resistance temperature of heterojunction and reducing, and under low temperature, electrical resistance range of temperature is larger, therefore utilizes the R-T curve under this state accurately to measure low temperature.
Thermometer of the present invention, measuring method is as follows:
Heterojunction pure resistance-diode combined temp meter of the present invention is first connected the Ag of heterojunction, Co upper/lower electrode and external circuit measurement instrument when measuring, and working circuit diagram as shown in Figure 2.Then the electrode of metal Ag of heterojunction is contacted to logical heat transfer, object under test and the heterogeneous uniform temp that has with object under test.
According to the temperature range of physics to be measured, select gear.High temperature is selected 1 gear, and low temperature is selected 2 gears.When getting to S1 gear, heterojunction, in low resistance state, shows metallic character, can measure high temperature, and when getting to S2 gear, now heterojunction, in high-impedance state, shows characteristic of semiconductor, can measure low temperature.
The temperature of corresponding different object under test, heterojunction has different resistance, so reometer registration can change along with the temperature change of object under test, and corresponding one by one.According to corresponding relation, can obtain temperature.
When measuring temperature within the scope of 5K-70K, utilize high resistance state to measure temperature, wherein the corresponding relation of resistance and temperature is:
I=E2/R。
When measuring temperature within the scope of 70K-300K, utilize low resistance state to measure temperature, wherein the corresponding relation of resistance and temperature is: R=51.35+0.068T, I=E1/R.
It is wide that heterojunction pure resistance-diode combined temp meter of the present invention can be measured temperature range, on a large scale, all can guarantee same measuring accuracy.The impressed voltage stimulation of ± 1V descends can realize two kinds of configurations the mutual conversion between two gears while being temperature survey, fast to the response time of temperature.From reometer, can read registration, and temperature is corresponding one by one.
Accompanying drawing explanation
The schematic diagram that Fig. 1 .Co (10nm)/CoO-ZnO (10nm)/Ag (60nm) heterostructure and electric resistance changing are measured.
Fig. 2 is thermometer work schematic diagram.E1, E2 are 1.5V batteries, and corresponding contactor is S1, S2.
Fig. 3. the I-V curve of embodiment 1 bipolar resistive random.Under the effect of forward voltage, from high-impedance state, become low resistance state, wherein Vset=+0.7V, embodiment, under the effect of negative voltage, becomes high-impedance state from low resistance state, wherein Vreset=-0.8V.When embodiment is in low resistance state, I-V curve is linear, shows as the character of pure resistance.
Fig. 4. the resistance R of embodiment 1 and the relation curve of temperature T.When embodiment is in low resistance state, the rising of electrical resistance temperature and increasing, shows as the character of metallic conduction; When embodiment is in high resistance state, the rising of electrical resistance temperature and reducing, shows as the character of semiconductor conduction.
Fig. 5 is the R-T curve under embodiment 1 high-impedance state.When measurement temperature is within the scope of 5K-70K, the resistance of high resistance state and the corresponding relation of temperature are: lnR=6.59+2.24*T
-1/4.
Fig. 6 is the R-T curve under embodiment 1 low resistance state.When measurement temperature is within the scope of 70K-300K, the resistance of low resistance state and the corresponding relation of temperature are: R=51.35+0.068T
Embodiment
Below in conjunction with embodiment, the present invention will be further described, but be not limited to this.
Embodiment 1:
The preparation of Co (10nm)/CoO-ZnO (10nm)/Ag (60nm) heterojunction:
Utilize the method for magnetron sputtering, at Grown upper/lower electrode and middle ZnO insulation course, and utilize stainless steel mask method to be prepared; Process conditions and step are as follows:
Sputtering chamber vacuum is evacuated to 7.5 × 10
-5pa, take purity as more than 99.95% ZnO pottery and more than 99.99% Co metal and Ag metal as target, ZnO is placed in to radio frequency target, Co and Ag are placed in respectively direct current target.Using purity as more than 99.99% high-purity Ar gas is as sputtering atmosphere, Ar gas enters sputtering chamber through gas meter.
The sputtering power of Co is 5W, and sputtering pressure is 0.58Pa.
The sputtering power of ZnO is 15W, and sputtering pressure is 0.65Pa.
The sputtering power of Ag is 5W, and sputtering pressure is 0.55Pa.
Above the glass substrate of water-cooled, place ground floor stainless steel mask, with metal clip by substrate bracket, glass substrate and mask fixedly prevent dislocation, deposit respectively 1.5nm Cr, 30nmAg, 10nm Co, wherein Cr is as cushion, Ag is electrode of metal, and Co is as the bottom electrode of heterojunction.
Be replaced by afterwards second layer stainless steel mask, sputtering sedimentation 10nm ZnO, wherein the growth atmosphere of ZnO is Ar gas and O
2the combination gas of gas, wherein oxygen volume ratio accounts for 5 ‰.Oxonium ion oxidation in the oxidized zinc of cobalt at ZnO and Co interface place forms CoO layer.
Then change the 3rd layer of stainless steel mask, sputter 60nm Ag is as electrode of metal.
Above-mentioned intermediate oxidation layer material is the ZnO that has a large amount of oxygen room, belongs to semiconductor material with wide forbidden band.
The present invention's backing material used is healthy and free from worry D 263 eco
tMt glass substrate.
The method of applied metal mask of the present invention is prepared heterojunction.The thickness of whole heterojunction is within 100nm.Heterojunction can be made into the miniature thermometer that area is less than 0.01 square millimeter, can be used for " point " thermometric, the i.e. temperature survey of micrometer range.
Heterogenous dual-pole resistive effect experiment:
Experimental technique: selected bottom electrode Co ground connection in measuring process.When top electrode Ag adds certain positive voltage, sample can become low resistance state from high-impedance state, and voltage is now called Vset.
When top electrode Ag adds certain negative voltage, sample can become high-impedance state from low resistance state, and voltage is now called Vreset.
Experimental result: (1), when sample is in high-impedance state, the rising of sample electrical resistance temperature and reducing, show semiconductor conductive characteristic, and low-temperature space electrical resistance range of temperature is larger, therefore can utilize the high-impedance state Measurement accuracy low temperature of sample.
(2) when sample is in low resistance state, the rising of the electrical resistance temperature of sample and increasing, shows metallic conduction characteristic, therefore can utilize the low resistance state of sample to measure high temperature.
Temperature survey
During measurement, the Ag of heterojunction, Co upper/lower electrode and external circuit measurement instrument are connected, in external circuit, are provided with S1, two switches of S2, respectively corresponding two reverse 1.5V battery supplies; When getting to 1 gear, voltage be silver just, cobalt is negative, oxonium ion is to run to zinc paste, in low resistance state, when getting to 2 gear, voltage is that silver is negative, cobalt just, oxonium ion is run to cobalt oxide, in high configuration.R-T curved measurement high temperature corresponding to metallic conduction characteristic while utilizing low resistance state, R-T curved measurement low temperature corresponding to semiconductor conductive characteristic while utilizing high resistance state, thus realize a thermometer and can measure the temperature range of 5K-300K.
Application examples: the water temperature that measurement temperature is 290K.
1 by switch S 1 closure, and thermometer is got to 1 gear.
2 fully contact heterojunction entirety with water, after temperature stabilization, and read current table data 0.021A.
3 according to R=51.35+0.068T, and I=E1/R relation can obtain, and temperature is 290k.
Claims (1)
1. heterojunction pure resistance-diode combined temp meter, is characterized in that adopting Co/CoO-ZnO/Ag heterojunction, and in this heterojunction, Co is bottom electrode, and Ag is top electrode, and CoO-ZnO is composite insulation layer;
When measuring, the Ag of heterojunction, Co upper/lower electrode and external circuit measurement instrument are connected, in external circuit, be provided with two gears, respectively corresponding two reverse battery power supplys; When voltage silver just, cobalt when negative heterojunction in low resistance state, R-T curved measurement high temperature corresponding to metallic conduction characteristic while utilizing low resistance state; When voltage is that silver is negative, cobalt timing heterojunction is in high configuration; R-T curved measurement low temperature corresponding to semiconductor conductive characteristic while utilizing high resistance state;
The measurement temperature range 5K-300K of described thermometer.
2, thermometer as claimed in claim 1, is characterized in that, when measuring temperature within the scope of 5K-70K, utilizes high resistance state to measure temperature, and wherein the corresponding relation of resistance and temperature is:
.
3, thermometer as claimed in claim 1, is characterized in that, when measuring temperature within the scope of 70K-300K, utilizes low resistance state to measure temperature, and wherein the corresponding relation of resistance and temperature is:
.
4, a preparation method of heterojunction Co/CoO-ZnO/Ag, utilizes magnetically controlled sputter method at Grown upper/lower electrode and middle ZnO insulation course, and process conditions and step are as follows:
Sputtering chamber vacuum is evacuated to 7.5 × 10
-5pa, the Co metal take purity as more than 99.95% ZnO pottery, purity more than 99.99% and the more than 99.99% Ag metal of purity, as target, are placed in radio frequency target by ZnO, and Co and Ag are placed in respectively direct current target; Using purity as more than 99.99% high-purity Ar gas is as sputtering atmosphere, Ar gas enters sputtering chamber through gas meter; The sputtering power of Co is 5W, and sputtering pressure is 0.58Pa; The sputtering power of ZnO is 15W, and sputtering pressure is 0.65Pa; The sputtering power of Ag is 5W, and sputtering pressure is 0.55Pa;
Above substrate, place ground floor stainless steel mask, deposit respectively 1 ~ 2nm Cr, 25 ~ 35nm Ag, 8 ~ 12nm Co, wherein Cr is as cushion, and Ag is electrode of metal, and Co is as the bottom electrode of heterojunction; Then replace with second layer stainless steel mask, the ZnO layer of sputtering sedimentation 8 ~ 12nm, the growth atmosphere of ZnO is Ar gas and O
2the combination gas of gas, wherein oxygen volume ratio is 5 ‰; Oxonium ion oxidation in the oxidized zinc of cobalt at ZnO and Co interface place forms CoO layer, and CoO layer is not Direct precipitation layer; Then replace with the 3rd layer of stainless steel mask, sputter 55 ~ 60nm Ag is as electrode of metal.
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| CN102687301A (en) * | 2010-02-22 | 2012-09-19 | 株式会社东芝 | Solar cell and method for manufacturing same |
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