CN101882463B - Multiposition ferroelectric memory and voltage application method thereof - Google Patents
Multiposition ferroelectric memory and voltage application method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of microelectronics, and relates to a multiposition ferroelectric memory and a voltage application method thereof. In the invention, a layer of uneven step-shaped ferroelectric film material with different thicknesses is constructed by utilizing the characteristic that the polarization reversal of the ferroelectric film material can occur only when an external electric field reaches a coercive field, each step corresponds to one thickness and further respectively corresponds to a certain coercive voltage, and the polarization reversal of the ferroelectric film material with the corresponding step thickness is carried out by applying different external voltages. A multiposition data storing function can be realized by combining the ferroelectric film materials with different step thicknesses in a single storage unit. A multiposition storage device processed by adopting the method of the invention can greatly improve the storage density and lower the production cost.
Description
Technical field
The invention belongs to microelectronics technology, be specifically related to a kind of multiposition ferroelectric memory and voltage application method thereof.
Background technology
Storer occupies critical role in semi-conductor market, according to investigations, only two kinds of DRAM (Dynamic RandomAccess Memory) and Flash just occupy 15% of whole market.Along with progressively popularizing of portable electric appts, the market of nonvolatile memory is also increasing, and Flash accounts for 90% of nonvolatile memory market at present.But along with the progress of semiconductor technology, Flash has run into increasing technical bottleneck, and tunnel oxide can not be along with the development of integrated circuit technology attenuate unrestrictedly, and according to ITRS 2007, Flash will be difficult to go beyond the 32nm process node.The thinking that addresses this problem is research and development nonvolatile memories of new generation, mainly contain magnetic store (MRAM), phase transition storage (PCM), Memister (ReRAM) and ferroelectric memory (FeRAM), wherein ferroelectric memory is realized commercialization at first, has very strong commercial potential quality.
The spontaneous polarization that ferroelectric memory utilizes ferroelectric material to have, and the character that can under External Electrical Field, reverse of spontaneous polarization vector and realize memory function.The disclosed ferroelectric memory of prior art generally adopts the material of perovskite structure series, for example lead zirconate titanate, the i.e. alloy (hereinafter to be referred as PZT) of Pb (Zr, Ti) O3.The principal character of this material is to have ferroelectricity, namely has the relation of ferroelectric hysteresis loop between electric polarization and the external electric field.This specific character makes it to be very suitable for doing storer, two states of its residual polarization are corresponding " 0 " and the one state of storer respectively, and can change store status or come its polarized state of sensing, reading information by peripheral circuit by the direction that changes external electric field.
Traditional ferroelectric storage cell adopts the structure of storehouse form usually, as shown in Figure 1.Take the 1T1C structure as example, its formation method generally is to form on the present silicon substrate 10 after transistorized grid 12, gate dielectric 14 and the source/drain regions 16, cover again last layer dielectric layer 20, then in dielectric layer 20, form the end that contact window plug 22 is connected to source/drain regions 16, form ferroelectric storage cell at contact window plug 22 at last.Traditional ferroelectric storage cell is with " planar fashion " storehouse from bottom to top, forms ferroelectric thin films 26 at the first electrode 24, and forms the second electrode 28 at ferroelectric thin film 26.This kind ferroelectric storage cell must provide enough areas of plane in order to keep enough electric capacitys, with the permanence that keeps storing data.Therefore, in order to realize the storage density of ferroelectric memory, on the one hand, can increase the integration density of ferroelectric storage cell; On the other hand, can in single storage unit, store long numeric data.
Obviously, when increasing the storage density of ferroelectric memory by front a kind of method, there is following shortcoming: along with the continuous increase of ferroelectric storage cell integration density, relatively, the usable area of ferroelectric storage cell will constantly dwindle, and tend to like this cause the problem of electric capacity deficiency.And a kind of method can improve storage density effectively after adopting under the prerequisite that does not reduce original ferroelectric storage cell usable area, thereby has reduced production cost widely.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, propose a kind of multiposition ferroelectric memory and voltage application method thereof, the present invention can realize the structure of ferroelectric memory multidigit storage, to improve storage density, reduces production costs.
The multiposition ferroelectric memory that the present invention proposes is by the uneven step-like ferroelectric thin-flim materials with multiple different-thickness of structure one deck, and the multidigit memory function that realizes storing long numeric data by the ferroelectric thin film that makes up different step thicknesses in single storage unit.It is characterized in that comprising step:
(1) deposit the first metal electrode membraneous material on silicon substrate;
(2) at the uneven step-like ferroelectric thin-flim materials with different-thickness of the first metal electrode preparation one deck;
(3) deposit the second metal electrode membraneous material on ferroelectric thin film.
Among the present invention, comprise nano impression in the uneven method with step-like ferroelectric thin film of different-thickness of the first electrode preparation one deck, mechanical stamping and advanced photoetching and etching technique.
Among the present invention, ferroelectric thin-flim materials comprises lead zirconate titanate, strontium bismuth titanate, bismuth lanthanum titanate, barium strontium and polyvinylidene fluoride base ferroelectric material; Described the first metal electrode comprises platinum, ruthenium, iridium, chromium billon and yttrium oxide; Described the second metal electrode comprises platinum, ruthenium, iridium, chromium billon and yttrium oxide.
Another object of the present invention is to provide the voltage application method of described multiposition ferroelectric memory, could realize polarization reversal because the ferroelectric thin film of different-thickness need apply the external voltage of different sizes, the ferroelectric thin film of n kind different-thickness is the external voltage of the different sizes of corresponding n kind successively.Take n=2 as example, n 〉=2 o'clock the like, concrete steps comprise:
(1) between the first electrode and the second electrode, apply a higher forward voltage V2, so that all reverse polarizations of ferroelectric thin film at two different step thicknesses places,, corresponding the first store status of this state;
(2) apply low reverse voltage-V1 between the first electrode and the second electrode, so that the ferroelectric thin film of step thicknesses smaller part is inverted to the forward polarization, the ferroelectric thin film reverse polarization of step thicknesses larger part keeps, corresponding the second store status of this state;
(3) between the first electrode and the second electrode, apply a higher negative voltage-V2, so that all forward polarization of the ferroelectric thin film at two different step thicknesses places, corresponding the 3rd store status of this state;
(4) apply a lower forward voltage V1 between the first electrode and the second electrode, so that the ferroelectric thin film of step thicknesses smaller part is inverted to reverse polarization, the polarization of the ferroelectric thin film forward of step thicknesses larger part keeps, corresponding the 4th store status of this state;
Voltage application method provided by the invention, the ferroelectric thin film of corresponding n kind different-thickness can realize 2
nIndividual store status (n 〉=2).
The structure of multiposition ferroelectric memory provided by the present invention and voltage application method thereof can improve storage density effectively, reduce production costs.
Description of drawings
Fig. 1 is the ferroelectric memory that prior art has the 1T1C planar structure.
Fig. 2 A-2D is the preparation process diagrammatic cross-section according to embodiments of the invention 1 (ferroelectric storage cell with two steps).
Fig. 3 is the diagrammatic cross-section according to embodiments of the invention 2 (ferroelectric storage cell with n＞2 step).
Fig. 4 A～4D is the voltage application method schematic diagram according to embodiments of the invention 1.
The ferroelectric materials electric hysteresis loop wire of Fig. 5 for adopting voltage application method provided by the present invention to obtain according to embodiments of the invention 1.
Fig. 6 be PZT material under a certain proportioning in this ferroelectric material electric domain reverse-poled size under 9 volts of voltages as reference, this ferroelectric film electric domain reverse-poled number percent that obtains and the graph of a relation of impressed voltage.
Number in the figure explanation: 100 silicon substrates, 102 first metal electrodes, 104 liang of rank ferroelectric thin films, the ferroelectric thin film at 104-1 first step place, the ferroelectric thin film at 104-2 second step place, 106 second metal electrodes, 200 silicon substrates, 202 first metal electrodes, 204n rank ferroelectric thin film, the ferroelectric thin film at 204-1 first step place, the ferroelectric thin film at 204-2 second step place, the ferroelectric thin film at place, 204-n n rank, 206 second metal electrodes.
Embodiment
Hereinafter more specifically describe the present invention in the reference example in conjunction with being shown in, the invention provides preferred embodiment, but should not be considered to only limit to embodiment set forth herein.In the drawings, for convenience of description, amplified the thickness in layer and zone, shown in size do not represent physical size.
Reference diagram is the schematic diagram of idealized embodiment of the present invention, and embodiment shown in the present should not be considered to only limit to the given shape in zone shown in the figure, but comprises resulting shape, the deviation that causes such as manufacturing.For example the curve that obtains of etching has crooked or mellow and full characteristics usually, but in embodiments of the present invention, all represents with rectangle, and the expression among the figure is schematically, but this should not be considered to limit the scope of the invention.
With reference to figure 2, be depicted as the diagrammatic cross-section of the ferroelectric storage cell with two steps.The first metal electrode 102 is formed on the silicon substrate 100, and the first metal electrode can be platinum, ruthenium, iridium, chromium billon and yttrium oxide.Pass through nano impression on the first metal electrode 102, mechanical stamping or advanced photoetching and etching technique prepare the ferroelectric thin film 104 that one deck has two steps, thinner first step partly is designated as 104-1, thicker second step partly is designated as 104-2, the thickness of two steps can and be executed alive size and carry out the optimization adjustment according to thickness and the polarization intensity of ferroelectric thin film, to obtain best store status.The step ferroelectric thin-flim materials can be lead zirconate titanate, strontium bismuth titanate, bismuth lanthanum titanate, barium strontium and polyvinylidene fluoride base ferroelectric material.Form the second metal electrode 106 at ferroelectric thin film 104 and can be platinum, ruthenium, iridium, chromium billon and yttrium oxide.
With reference to figure 3, be depicted as the diagrammatic cross-section of the ferroelectric storage cell of (n＞2) the individual step that has n.Unique difference of Fig. 3 and Fig. 2 is that the ferroelectric thin film number of steps among Fig. 3 will be higher than the ferroelectric thin film number of steps among Fig. 2.The thickness of each step can carry out the optimization adjustment according to the thickness of ferroelectric thin film and the relation of coercive voltage, to obtain best store status.
Embodiment 3
With reference to figure 2A～2D.
Fig. 2 A is that the first metal electrode 102 is formed at silicon substrate 100 cross-sectional view afterwards.Selected Si substrate 100 is low-drag type (111) silicon chip, first with the ultrasonic surface organic matter that removes of acetone, use dense H2SO4: H2O2=1: 1 is heated to about 100 degree again, and kept 5 to 10 minutes, do with the deionized water punching more afterwards and dry, retell silicon chip and put into water: HF=10: 1 solution soaked about 20 minutes, remove oxide on surface, do with the deionized water punching afterwards and dry, retell silicon chip and put into NH4OH: H2O2: H2O=1: the I solution of 2: 5 volume ratios boiled 5 minutes, do with the deionized water punching afterwards and dry, again silicon chip is put into HCL: H2O2: H2O=1: the II liquid of 2: 8 volume ratios boiled 10 minutes, did afterwards drying with the deionized water punching; Deposit the first metal electrode material 102 on cleaned silicon chip, such as platinum, ruthenium, iridium, chromium billon and yttrium oxide.
Fig. 2 B is the cross-sectional view behind the first metal electrode 102 preparation one deck ferroelectric thin-flim materialss 104, and ferroelectric thin-flim materials can be lead zirconate titanate, strontium bismuth titanate, bismuth lanthanum titanate, barium strontium and polyvinylidene fluoride base ferroelectric material.This example uses sol-gel process to prepare ferroelectric lead zirconate titanate film.By certain stoichiometric proportion, take lead acetate, methyl alcohol, butyl titanate, propyl alcohol zirconium, acetic acid as starting material, be mixed and made into lead zirconate titanate colloidal sol elder generation body by heating water bath.With 3000r/min, on the first metal electrode 102, use spin coater spin coating lead zirconate titanate colloidal sol elder generation body 30 seconds, then its hot plate at 175 degrees centigrade heated 3 minutes, and last hot plate at 350 degrees centigrade heated 5 minutes, thereby obtained one deck ferroelectric thin film.Use the same method, obtain in rapid thermal anneler, to anneal 15 minutes with 650 degrees centigrade after the second layer ferroelectric thin film.On second layer ferroelectric thin film, with 3000r/min spin coating lead zirconate titanate colloidal sol elder generation body 30 seconds, wait for 3 minutes with spin coater, obtain the 3rd layer of ferroelectric thin film, spin coating is 6 times and so forth.Heated 5 minutes at 50 degrees centigrade of hot plates afterwards, thereby finally obtain ferroelectric thin film 104.
The cross-sectional view of Fig. 2 C after for the ferroelectric thin film that the ferroelectric thin film 104 for preparing is processed into thinner 104-1 step and thicker two different-thickness of 104-2 step, job operation can be nano impression, mechanical stamping and advanced photoetching and etching technique.This example adopts nano-imprinting method to be processed to form the ferroelectric thin film 104 concave-convex surface patterns shown in Fig. 2 C.Be specially and adopt the silicon template of certain live width and the optical grating construction in cycle to impress ferroelectric thin film 104, under certain pressure, keep 15 minutes after, take off the silicon template, just form the concave-convex surface pattern of the ferroelectric thin film 104 shown in Fig. 2 C.Then will carry out heating anneal with the ferroelectric thin film 104 of concavo-convex pattern, namely finish the surface topography processing of ferroelectric thin film.
Fig. 2 D is the cross-sectional view after step-like ferroelectric thin film forms the second metal electrode 106.The second metal electrode material 102 comprises platinum, ruthenium, iridium, chromium billon and yttrium oxide.
Embodiment 4
With reference to figure 4A～4D.
Fig. 4 A～4D is the foundation voltage application method schematic diagram with ferroelectric storage cell of 2 steps of the present invention.
Because ferroelectric material is originally in not having under the impressed voltage existence residual polarization is arranged, the ferroelectric thin film upper and lower surface will be adsorbed positive and negative charge according to principle of opposite sex attraction, externally then do not show potential difference (PD), in the time of when impose on ferroelectric material two surface electrodes with certain voltage on, the electricdomain of ferroelectric thin-flim materials inside will be reversed, the electric charge of adsorption will be ostracised and be flowed in peripheral circuit at this moment, thereby give the peripheral circuit current signal, the memory function that realization is read and write. without the finished ferroelectric material of the present invention, its electricdomain will be reversed rapidly under certain voltage, ferroelectric thin-flim materials PZT under a certain proportioning is as example, certain thickness this ferroelectric thin film is measured under the voltage of 1 volt of voltage to 9 volt, this PZT ferroelectric material electric domain reverse-poled size is as reference under 9 volts of voltages, can obtain ferroelectric film electric domain under 4V voltage, only have 11.47% reverse-poled number percent, and the reverse-poled number percent of ferroelectric film electric domain reached for 87% (as shown in Figure 6) under the 5V voltage.Namely when impressed voltage was lower than coercive voltage, the polarization reversal of minute quantity only occured in ferroelectric film electric domain; And when impressed voltage was higher than coercive voltage, ferroelectric film electric domain was with most of polarization reversal.And the ferroelectric thin film correspondence of different-thickness different coercive voltages, therefore can realize by making up uneven step-like ferroelectric thin-flim materials with different-thickness the multidigit memory function of ferroelectric memory.
Take two stage rank ferroelectric thin films as example, film both sides electrode voltage is added to necessarily, be made as V2, whole ferroelectric film electric domain is with reverse polarization, and this is defined as store status (00).Impressed voltage-V1, then the electricdomain than thin ferroelectric film will be inverted to the forward polarization, and the electricdomain of thicker ferroelectric thin film keeps reverse polarization, this defines store status (01).All forward polarization of impressed voltage-V2, the ferroelectric thin film at two different step thicknesses places, this moment, this defined store status (11).Impressed voltage V1, then the electricdomain than thin ferroelectric film will be inverted to reverse polarization, and the electricdomain of thicker ferroelectric thin film keeps the forward polarization, this defines store status (10).Owing to finishing under a voltage without its polarization reversal of the finished ferroelectric thin-flim materials of the inventive method, be made as V, ferroelectric media material storage this moment only have two states (V and-V), the ferroelectric media film of constructing via the present invention so will have by original binary states and become one of four states (V2,-V1,-V2, V1).So just can be used for defining four storage attitudes (00,01,11,10), thereby realize 4 storages under same unit.
Embodiment 5
The below is take the foundation embodiment of the invention (ferroelectric storage cell with 2 steps) as example, gathers the voltage application method of ferroelectric four store statuss of realization that concrete diagram illustrates.
Fig. 4 A is for to apply a higher forward voltage V2 between the first metal electrode 102 and the second metal electrode 106, the first metal electrode 102 ground connection, and the second metal electrode 106 meets forward voltage V2.Under this forward voltage, all reverse polarizations of ferroelectric thin film at first step 104-1 and second step 104-2 place, corresponding the first store status of this state;
Fig. 4 B hangs down negative voltage-V1 for apply one between the first metal electrode 102 and the second metal electrode 106, the first metal electrode 102 ground connection, and the second metal electrode 106 meets negative voltage-V1.The ferroelectric film electric domain at thinner first step 104-1 place will be inverted to the forward polarization, and the ferroelectric thin film at thicker second step 104-2 place keeps reverse polarization, corresponding the second store status of this state;
Fig. 4 C applies a higher negative voltage-V2 between the first metal electrode 102 and the second metal electrode 106, the first metal electrode 102 ground connection, and the second metal electrode 106 meets negative voltage-V2.Under this negative voltage, the ferroelectric thin film at first step 104-1 and second step 104-2 place all is inverted to the forward polarization, corresponding the 3rd store status of this state;
Fig. 4 D is for to apply one than low forward voltage V1 between the first metal electrode 102 and the second metal electrode 106, the first metal electrode 102 ground connection, and the second metal electrode 106 meets forward voltage V1.The ferroelectric film electric domain at thinner first step 104-1 place will be inverted to reverse polarization, and the ferroelectric thin film at thicker second step 104-2 place keeps the forward polarization, corresponding the 4th store status of this state;
Owing to finishing under a voltage without its polarization reversal of the finished ferroelectric thin-flim materials of the inventive method, be made as V, ferroelectric media material storage this moment only have two states (V and-V), the ferroelectric media film of constructing via the present invention so will have by original binary states and become one of four states (V2,-V1,-V2, V1).So just can be used for defining four storage attitudes (00,01,11,10), thereby realize 4 storages under same unit.
Figure 5 shows that the ferroelectric materials electric hysteresis loop wire that adopts voltage application method provided by the present invention to obtain according to embodiments of the invention.
Add external voltage V2, whole ferroelectric film electric domain is reverse polarization, corresponding ferroelectric thin film surface charge state Q (00), i.e. the first store status (00).Impressed voltage-V1, then the electricdomain than thin ferroelectric film will be inverted to the forward polarization, and the electricdomain of thicker ferroelectric thin film keeps reverse polarization, and corresponding ferroelectric thin film surface charge state Q (01), this defines store status (01).All forward polarization of impressed voltage-V2, the ferroelectric thin film at two different step thicknesses places, corresponding ferroelectric thin film surface charge state Q (11), this defines store status (11).Impressed voltage V1, then the electricdomain than thin ferroelectric film will be inverted to reverse polarization, and the electricdomain of thicker ferroelectric thin film keeps the forward polarization, and corresponding ferroelectric thin film surface charge state Q (10), this defines store status (10).Thereby four storage attitudes (00,01,11,10) that obtain defining.
Embodiment 7
Fig. 6 be PZT material traditional under a certain proportioning in this ferroelectric material electric domain reverse-poled size under 9 volts of voltages as reference, the ferroelectric film electric domain reverse-poled number percent that obtains and the graph of a relation of impressed voltage.Result's demonstration, ferroelectric film electric domain only have 11.47% reverse-poled number percent, and the reverse-poled number percent of ferroelectric film electric domain has reached 87% under the 5V voltage under 4V voltage.
In the situation that can also consist of without departing from the spirit and scope of the present invention many very embodiment of big difference that have.Should be appreciated that except as defined by the appended claims, the invention is not restricted at the specific embodiment described in the instructions.
Claims (6)
1. voltage application method that is used for multiposition ferroelectric memory, described multiposition ferroelectric memory contains a plurality of ferroelectric storage cells, each ferroelectric storage cell contains silicon substrate, the first metal electrode membraneous material is arranged on the silicon substrate, step-like ferroelectric thin-flim materials and the second metal electrode membraneous material, make up the step-like ferroelectric thin-flim materials with different-thickness by the step-like ferroelectric thin-flim materials that has different-thickness at the first metal electrode preparation one deck, and by certain voltage application method, realize the multidigit memory function of storage long numeric data in single ferroelectric storage cell, it is characterized in that, in the described voltage application method, for the ferroelectric thin film of the n kind different-thickness successively external voltages of the different sizes of corresponding n kind, wherein n 〉=2; In the n=2 situation, comprise the steps:
(1) between the first metal electrode and the second metal electrode, apply a higher forward voltage V2, so that all reverse polarizations of ferroelectric thin film at two different step thicknesses places, corresponding the first store status of this state;
(2) between the first metal electrode and the second metal electrode, apply low negative voltage-Vl, so that the ferroelectric thin film of step thicknesses smaller part is inverted to the forward polarization, the ferroelectric thin film reverse polarization of step thicknesses larger part keeps, corresponding the second store status of this state;
(3) between the first metal electrode and the second metal electrode, apply a higher negative voltage-V2, so that all forward polarization of the ferroelectric thin film at two different step thicknesses places, corresponding the 3rd store status of this state;
(4) between the first metal electrode and the second metal electrode, apply a lower forward voltage Vl, so that the ferroelectric thin film of step thicknesses smaller part is inverted to reverse polarization, the ferroelectric thin film forward polarization of step thicknesses larger part keeps, corresponding the 4th store status of this state;
In the situation that n＞2, the impressed voltage that the step of different thickness is corresponding different, the thickness of each step carries out the optimization adjustment according to the thickness of ferroelectric thin film and the relation of coercive voltage, to obtain best store status.
2. method according to claim 1 is characterized in that: the described method that has a step-like ferroelectric thin-flim materials of different-thickness at the first metal electrode preparation one deck is selected from nano impression, mechanical stamping or advanced photoetching and etching technique.
3. method according to claim 1 and 2, it is characterized in that: described ferroelectric thin-flim materials comprises lead zirconate titanate, strontium bismuth titanate, bismuth lanthanum titanate, barium strontium and polyvinylidene fluoride base ferroelectric material.
4. method according to claim 1 and 2 is characterized in that, described the first metal electrode is platinum, nail, iridium, chromium gold or yttrium oxide.
5. method according to claim 1 and 2 is characterized in that, described the second metal electrode is platinum, nail, iridium, chromium gold or yttrium oxide.
6. method according to claim 1 is characterized in that, the ferroelectric thin film of described n kind different-thickness realizes 2
nIndividual store status.
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