CN101290972B - Erasable and readable thin film type resistor switching device and preparing method thereof - Google Patents
Erasable and readable thin film type resistor switching device and preparing method thereof Download PDFInfo
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- CN101290972B CN101290972B CN2008100385795A CN200810038579A CN101290972B CN 101290972 B CN101290972 B CN 101290972B CN 2008100385795 A CN2008100385795 A CN 2008100385795A CN 200810038579 A CN200810038579 A CN 200810038579A CN 101290972 B CN101290972 B CN 101290972B
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- thin film
- sulphur cyanogen
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Abstract
The invention belongs to the microelectronic device and functional thin film technical field, and in particular relates to an erasable and readable thin film type resistor switch and a method for making the same. The device has a structure of M1-Functional layer-M2 with metal layers on two ends serving as electrodes, wherein the functional layer is polythiocyanogen thin film formed by spontaneouscuring on the basis of the thiocyanogen film deposited by solution absorption. The thin film device with the structure has stable reversible resistance switch characteristics, with the resistance radio of a high resistance state to a low resistance state being between 10<3> and 10<6>, and can be used as a switch device and a storage device. In addition, the manufacturing process of the device is very simple.
Description
Technical field
The invention belongs to microelectronic component and function film technical field, be specifically related to a kind of erasable, the thin film type resistor switching device that can read and preparation method thereof.
Technical background
Have the dual stabilization part of resistance switch characteristic owing to have the stable state of two kinds of different resistance values, can be used as switch and memory device uses, this respect has vast market prospect, has caused the great attention of academia and industrial circle.In the art, the technology of developing high performance material and simple possible has become the direction that the research staff makes great efforts.
Sulphur cyanogen is a kind of typical pseudohalogen, is yellow liquid, and molecular formula is: (SCN)
2If make solvent with ether or carrene, sulphur cyanogen solution is can stable existence below 0 ℃.In research process, we find that sulphur cyanogen is very easy in copper film surface adsorption film forming, at the next spontaneous thin polymer film that is solidified into of drying at room temperature condition.Through careful exploratory development, we find that this cured film not only has very high stability, and the function medium layer that can be used as electronic device uses.
For this reason, the present invention proposes erasable, the thin film type resistor switching device that can read based on sulphur cyanogen cured film.We also develop and a kind of extreme simple manufacture method, and this simple process is highly beneficial for practical application.In addition because hearth electrode adopts copper, therefore can with the copper-connection compatibility in the microelectric technique.
Summary of the invention
The objective of the invention is to propose a kind of erasable, the thin film type resistor switching device that can read and preparation method thereof.
The thin film type resistor switching device that the present invention proposes is erasable, can read adopts sandwich, as shown in Figure 1.The structure of device is followed successively by: metallic bottom electrode (M
1), function medium layer, metal roof electrode (M
2), i.e. metal-function medium layer-metal (M
1-Functional layer-M
2) structure.Wherein, the metal level (M of two ends
1And M
2) as electrode.This device can excite by forward and reverse potential pulse and realize writing and wiping of signal, reads with the small voltage pulse signal.
The concrete structure of the thin film type resistor switching device that the present invention also proposes is erasable, can read: hearth electrode adopts copper film (Cu), and thickness is 150nm-300nm; Top electrode adopts aluminium film (Al), and thickness is 80nm-150nm; Middle function medium layer is poly-sulphur cyanogen film, and function medium strata sulphur cyanogen (polythiocyanogen) film is formed by the spontaneous curing of sulphur cyanogen film.Be that device of the present invention is the Cu-polythiocyanogen-Al structure.
The preparation method of the thin film type resistor switching device that the present invention also proposes is erasable, can read: hearth electrode wherein (Cu) and top electrode (Al) adopt vacuum thermal evaporation method film forming; Middle function medium layer adopts the copper hearth electrode to adsorb sulphur cyanogen film forming in sulphur cyanogen solution, passes through solvent clean then, allows the adsorbed film spontaneous curing form poly-sulphur cyanogen function medium layer again.
The present invention proposes need to prepare sulphur cyanogen solution in advance before the poly-sulphur cyanogen function medium layer of preparation, and is specific as follows: at (0 ℃--10 ℃) below 0 ℃, the sulphur cyanogen liquid that chemical synthesis is obtained is dissolved in ether or the carrene, and wiring solution-forming is preserved standby; Before use, with ether or ethanol this solution being diluted to concentration is 10
-1～10
-5M, temperature maintenance is below 0 ℃.
It is as follows that the present invention proposes the making step of thin film type resistor switching device: the copper film that evaporation one deck is thicker on smooth insulated substrate is as hearth electrode (thickness 150～300 nanometers); (sulphur cyanogen solution concentration is 10 in being immersed in hearth electrode through the sulphur cyanogen solution that dilutes below 0 ℃ then
-1～10
-5M), (solution concentration is big, and soak time is short to soak 3 minutes～10 hours; Solution is rare, needs relatively long soak time), take out the copper hearth electrode, use a large amount of solvent wash, natural airing or dry up with hair dryer was placed in the atmospheric environment of cleaning 2～10 hours; On hearth electrode, form poly-sulphur cyanogen film; Then on poly-sulphur cyanogen film the evaporation aluminium lamination as top electrode (thickness 80～150 nanometers).The size of each device can be determined according to concrete mask.It is 0.2-0.3mm that the cross-lapping department of copper hearth electrode and aluminium top electrode is divided into an area
2The size of thin-film device.
Resistance switch of the present invention is clamored basic structure with common consistent, and promptly hearth electrode is horizontal strip, and is evenly distributed, top electrode is a longitudinal strip, evenly distributed, a switching device is formed in the crosspoint in length and breadth of hearth electrode and top electrode, and area is 0.2-0.3 square millimeter (mm
2).A switching device array is formed in all hearth electrodes and top electrode crosspoint.
The thin film type resistor switching device that the present invention proposes has two kinds of different Resistance states (high-resistance state and low resistance state), but drives inverse conversion with the applied voltage signal between high-resistance state and the low resistance state, reads with very low voltage signal.Connect the positive pole in external signal source at copper electrode, under the situation of aluminium electrode grounding, after the forward voltage pulse signal excited, device was in low resistance state, is equivalent to write state, i.e. one state; After the reverse voltage pulse signal excitation, device is in high resistance state, is equivalent to erase status, i.e. " 0 " attitude; But the inverse conversion of two kinds of states realizes by alternately applying forward and reverse potential pulse.Two kinds of resistance states are read with lower voltage signal.Forward writes voltage and adopts 1.5～2.5 volts, and oppositely erasing voltage adopts-1.5～-3.0 volts; It is lower to read voltage, adopts 0.1～0.3 volt usually.
The thin film type resistor switching device good stability that the present invention proposes, the resistance value ratio of two kinds of resistance states is 10
3～10
6" writing-read-wipe-read " operation can repeatedly repeat, and can reach usually more than thousands of times.This thin-film device can be used as switch element and electrical storage device in information processing and computing Application for Field.Particularly, because structure and technology are simple, cost is extremely low, and is with practical value at mobile phone and MP3 technical field.
Description of drawings
The structural representation of Fig. 1 thin film type resistor switching device.
Fig. 2 is the current-voltage characteristic curve of the thin-film device of embodiment 1.
Fig. 3 is " writing-read-wipe-read " cycling (write for 2 volts ,-2.5 volts of wipings are read for 0.1 volt) of the thin-film device of embodiment 1.
Fig. 4 reads characteristic for two kinds of states of thin-film device of embodiment 1 read continuing under the voltage effect at 0.1 volt.
The current-voltage characteristic curve of the thin-film device of Fig. 5 embodiment 2.
" writing-read-wipe-read " cycling of the thin-film device of Fig. 6 embodiment 2 (write for 1.5 volts ,-2.0 volts of wipings are read for 0.1 volt).
Two kinds of states of the thin-film device of Fig. 7 embodiment 2 read continuing under the voltage effect at 0.1 volt and read characteristic.
The current-voltage characteristic curve of the thin-film device of Fig. 8 embodiment 3.
" writing-read-wipe-read " cycling of the thin-film device of Fig. 9 embodiment 3 (write for 1.5 volts ,-1.5 volts of wipings are read for 0.1 volt).
Two kinds of states of the thin-film device of Figure 10 embodiment 3 read continuing under the voltage effect at 0.1 volt and read characteristic.
The current-voltage characteristic curve of the thin-film device of Figure 11 embodiment 4 (can only write, can not wipe).
Number in the figure: 1 is substrate; 2 is the copper hearth electrode; 3 are poly-sulphur cyanogen function medium layer; 4 is the aluminium top electrode
Embodiment
Below by embodiment, further describe the preparation of the Cu-polythiocyanogen-Al device hearth electrode of the present invention's proposition:
Wave carrier piece with cleaning is substrate, 10
-3Under the pressure of Pa magnitude with the method evaporation thickness of vacuum thermal evaporation be the copper film of 200 nanometers as hearth electrode, the shape of copper hearth electrode is determined by mask.(in order to increase the adhesive force of copper hearth electrode and insulating glass substrate, can be before copper steam-plating first evaporation skim chromium.)
Below 0 ℃, standby sulphur cyanogen solution is diluted to 2.2 * 10 with ethanol
-2Mol/L gets 10 milliliters of these solution and places measuring cup, and the copper hearth electrode is immersed in this solution.Take out the hearth electrode sample after 6 minutes, with a large amount of ethanol washings, natural airing in the atmospheric environment of cleaning, room temperature was placed 2 hours.Place vacuum coating equipment then, the aluminium film of evaporation 100 nanometer thickness is as top electrode, and the shape of top electrode is controlled by mask.The area of copper hearth electrode and aluminium top electrode juxtaposition part is about 0.2～0.3 square millimeter.(the Raman stave is levied and is confirmed that sulphur cyanogen is in copper electrode surface adsorption film forming.)
Connect the positive pole in external signal source at copper electrode, under the situation of aluminium electrode grounding, the current-voltage characteristic curve of device (I-V) illustrates that this device has typical reversible bistable characteristic as shown in Figure 2.
" writing-read-wipe-read " characteristic of device realizes that with the applying pulse voltage signal pulse voltage signal is produced by the HP33120 function generator of computer control, with the current signal of Keithley2400 sampler.As shown in Figure 3, this device can write towards voltage signal with 2 deep-sited pulses, reads towards voltage signal with-2.5 deep-sited pulses, and two kinds of states are read with 0.1 volt of small voltage signal.This " writing-read-wipe-read " circulation can repeatedly repeat continuously, and stability is very good.
We have also tested the stability of write state and erase status, with the 4000 second time of 0.1 volt of small voltage continuous action, are equivalent to continue to read 4000 second time respectively, and two kinds of states remain unchanged separately, as shown in Figure 4; Read these two kinds of states in a few days more respectively and still remain unchanged, illustrate that two kinds of states of this class device are highly stable.
The solution that is used to soak the copper hearth electrode adopts 10 milliliter 2.1 * 10
-4The sulphur cyanogen solution of mol/L, soak time adopted 1 hour.Similar among processing step and method of measurement and the embodiment 1.The thin-film device that makes has stable reversible resistance switching characteristic equally, and is similar among the essential characteristic of current-voltage characteristic curve and the embodiment 1, but slight change is arranged on the details, as shown in Figure 5." write-read-wipe-read " circulation and also can repeatedly repeat continuously, as shown in Figure 6.The high-resistance state of device and low resistance state still can keep stable reading under the voltage effect, as shown in Figure 7.
The solution that is used to soak the copper hearth electrode adopts 10 milliliter 2.1 * 10
-4The sulphur cyanogen solution of mol/L, but soak time changes 5 hours into.Similar in processing step and method of measurement and embodiment 1 and 2.Current-voltage characteristic curve as shown in Figure 8." write-read-wipe-read " circulation and also can repeatedly repeat continuously, as shown in Figure 9.Two kinds of states of device still keep stable reading under the voltage effect, as shown in figure 10.
The solution that is used to soak the copper hearth electrode adopts 10 milliliter 2.1 * 10
-4The sulphur cyanogen solution of mol/L, but soak time changes 10 minutes into.Processing step and method of measurement and previous embodiment are similar.Experimental results show that this device can write with the forward voltage signal, but be difficult to wipe, as shown in figure 11 with reverse voltage signal.The performance of device is different with aforementioned several embodiment.
The present embodiment explanation, if solutions employed is very rare, the necessary long enough of soak time.When solution concentration was bigger, soak time can be very short, got final product in 6 minutes such as adopting among the embodiment 1, even can be shorter.
Claims (2)
1. erasable thin film type resistor switching device of reading, it is characterized in that this device architecture composition is followed successively by: metallic bottom electrode, function medium layer, metal roof electrode, here, metallic bottom electrode is a copper film, thickness is 150nm-300nm, the metal roof electrode is the aluminium film, and thickness is 80nm-150nm; The function medium layer is to adsorb sulphur cyanogen by the copper hearth electrode in sulphur cyanogen solution, then the poly-sulphur cyanogen film of spontaneous curing formation.
2. the preparation method of an erasable thin film type resistor switching device of reading as claimed in claim 1, it is characterized in that concrete steps are: on smooth insulated substrate, use vacuum thermal evaporation method evaporation copper film, make hearth electrode, copper film thickness is 150nm-300nm; Below 0 ℃, the diethyl ether solution or the dichloromethane solution of configuration sulphur cyanogen; Being diluted to concentration with ethanol below 0 ℃ is 10
-1～10
-5Mol/l; The copper hearth electrode is immersed in the above-mentioned solution, soaked 3 minutes～10 hours; Take out the copper hearth electrode, with the abundant drip washing of a large amount of ethanol, natural airing or dry up with hair dryer; Spontaneous curing 2～10 hours in the atmospheric environment of cleaning then forms poly-sulphur cyanogen film on the copper hearth electrode; Utilize vacuum thermal evaporation method deposition of aluminum film as top electrode at last, the aluminium film thickness is 80nm-150nm.
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|---|---|---|---|
| CN2008100385795A CN101290972B (en) | 2008-06-05 | 2008-06-05 | Erasable and readable thin film type resistor switching device and preparing method thereof |
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| CN101290972A CN101290972A (en) | 2008-10-22 |
| CN101290972B true CN101290972B (en) | 2010-11-17 |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317836A (en) * | 2001-02-20 | 2001-10-17 | 复旦大学 | Bi-stable electric organic film with polarity memorizing effect and its application |
| CN1540667A (en) * | 2003-10-30 | 2004-10-27 | 复旦大学 | Electricity writing in and heat erasable organic electric bistable thin film, and applicaton |
| CN101101963A (en) * | 2007-08-02 | 2008-01-09 | 复旦大学 | A high status ratio inorganic film dual stabilization part and its making method |
| CN101106172A (en) * | 2007-07-26 | 2008-01-16 | 复旦大学 | An erasable and readable inorganic film electrical dual stabilization part and its making method |
-
2008
- 2008-06-05 CN CN2008100385795A patent/CN101290972B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1317836A (en) * | 2001-02-20 | 2001-10-17 | 复旦大学 | Bi-stable electric organic film with polarity memorizing effect and its application |
| CN1540667A (en) * | 2003-10-30 | 2004-10-27 | 复旦大学 | Electricity writing in and heat erasable organic electric bistable thin film, and applicaton |
| CN101106172A (en) * | 2007-07-26 | 2008-01-16 | 复旦大学 | An erasable and readable inorganic film electrical dual stabilization part and its making method |
| CN101101963A (en) * | 2007-08-02 | 2008-01-09 | 复旦大学 | A high status ratio inorganic film dual stabilization part and its making method |
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