EP1913372A1 - Capteur a semi-conducteurs a large ecart energetique presentant une couche superieure isolante - Google Patents

Capteur a semi-conducteurs a large ecart energetique presentant une couche superieure isolante

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Publication number
EP1913372A1
EP1913372A1 EP06776682A EP06776682A EP1913372A1 EP 1913372 A1 EP1913372 A1 EP 1913372A1 EP 06776682 A EP06776682 A EP 06776682A EP 06776682 A EP06776682 A EP 06776682A EP 1913372 A1 EP1913372 A1 EP 1913372A1
Authority
EP
European Patent Office
Prior art keywords
sensor according
semiconductor sensor
electronic component
semiconductor
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06776682A
Other languages
German (de)
English (en)
Inventor
Mike Kunze
Ingo Daumiler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Microgan GmbH
Original Assignee
Microgan GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Microgan GmbH filed Critical Microgan GmbH
Publication of EP1913372A1 publication Critical patent/EP1913372A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/414—Ion-sensitive or chemical field-effect transistors, i.e. ISFETS or CHEMFETS

Definitions

  • the present invention relates to a semiconductor sensor for determining physical and / or chemical properties of a medium.
  • fluids in particular liquids or gases, are referred to as the medium.
  • the present invention relates to a pH sensor for determining the pH of a liquid.
  • the basis for such sensors are electronic semiconductor components, in the present case based on so-called "wide bandgap semiconductors" or semiconductors with a large band gap, wherein the band gap is> 2 eV
  • Such semiconductors are, for example, in the material systems gallium nitride (US Pat.
  • field-effect transistors for example HEMT, MODFET, MESFET or so-called ⁇ -FET (volume semiconductors with pulse-shaped doping profile) are suitable as embodiments for the semiconductor components.
  • Semiconductor materials suitable as bulk material for such electronic components.
  • HEMT a high electron mobility transistor
  • MODFET modulation-doped field effect transistor
  • MESFET metal-semiconductor field-effect transistor
  • ⁇ -FET MESFET in which a doping pulse with a high concentration was placed near the surface
  • SIT static induction transistor
  • HBT heterostructure bipolar transistor
  • Such an ion-sensitive semiconductor sensor is shown, for example, in DE 100 62 044 A1.
  • This sensor has a field effect transistor with a heterostructure of group III nitrides, which is formed as a HEMT structure.
  • the uppermost layer of the layer sequence comes into direct contact with the medium to be measured during the measurement.
  • a functional layer which selectively passes certain ions to be determined.
  • the transmitted ions occur on the gate surface or GaN surface of the layer sequence and trigger there directly the sensor effect.
  • ion exchangers e.g. Zeolites, proposed.
  • a conductive ceramic which is selectively permeable to ionized hydrogen atoms, to the uppermost layer of the devices.
  • Suitable material for this purpose are the materials known under the name Ormocere. lien.
  • a III-V semiconductor such as GaN or AlGaN is outstandingly suitable due to its polarity and the surface charges in order to achieve a pH sensitivity to solutions or other media.
  • the semiconductor sensor has an electronic component with a sensitive surface.
  • the electronic component is based on semiconductors with a large band gap, in particular of III-V semiconductors.
  • the sensitive surface is at least partially coated with a functional layer sequence, wherein the functional layer sequence in turn has an ion-sensitive surface, however, for the medium and / or the ions or substances to be determined is impermeable.
  • the uppermost layer of the functional layer sequence is chemically resistant. Furthermore, it is of considerable advantage if at least one of the layers of the functional layer sequence acts as at least ion-selective diffusion barrier layer for the ions to be determined.
  • Semiconductors with a large band gap such as, for example, diamond, gallium nitride (GaN) or silicon carbide (SiC), are particularly advantageously used for the semiconductor sensors according to the invention.
  • GaN gallium nitride
  • SiC silicon carbide
  • a functional layer or layer sequence is therefore applied to the sensitive layer according to the invention. It merely fulfills an intermediary role to the surface of the semiconductor component, wherein it is not permeable, for example, to the ions or substances themselves to be measured, for example hydrogen ions.
  • the electronic components can be constructed laterally or vertically. Various types of transistors are suitable for this purpose, for example HEMT, MODFET, MESFET, ⁇ -FET or also HBT.
  • the gate electrode is formed by the sensitive surface of the electronic component, possibly in conjunction with the medium located above the functional layer sequence.
  • Suitable materials for the sensitive surface of the electronic component are aluminum nitride, gallium nitride, indium nitride or aluminum gallium nitride of the formula Al x Gai -x N or indium gallium nitride of the formula In x Ga 1-x N, where 0.01 ⁇ x ⁇ 0.3.
  • Another material is indium aluminum nitride In x Al x . X N, where 0 ⁇ x ⁇ l.
  • the uppermost or another layer of the functional tional layer sequence which chemically possible inert, should be impermeable chemically stable and for the medium or ions or substances that are suitable oxides, especially metal oxides such as titanium oxide (TiO 2), alumina (Al 2 O 3 ), magnesium oxide (MgO), iron oxide (Fe 2 O 3 ), chromium-titanium oxide (Cri, 8 Ti 0 , 2 O 3 ), tungsten oxide (WO 3 ), indium oxide (In 2 O 3 ), or Lanthanum iron oxide " (LaFeO 3 ), or metals, ceramics or nitride-based materials such as titanium nitride or silicon nitride .Carbon-containing compounds such as diamond or diamond-like carbon (DLC) are suitable for this purpose.
  • metal oxides such as titanium oxide (TiO 2), alumina (Al 2 O 3 ), magnesium oxide (MgO), iron oxide (Fe 2 O 3 ), chromium-titan
  • an adhesion-promoting layer can be arranged in order to bond the functional layer sequence better to the electronic component.
  • Suitable materials for the adhesion-promoting layer include titanium, aluminum, titanium-tungsten alloys, silicon or various polymers.
  • the entire sensor can be encapsulated with the exception of its sensitive surface. This can be done, for example, by casting in epoxy resin and / or in polyimides.
  • the electronic component may be arranged directly or via intermediate layers on a substrate, for example of silicon, sapphire, silicon carbide, diamond, iridium or the like.
  • a buffer interlayer for example of gallium nitride, aluminum nitride, aluminum gallium nitride, diamond and / or combinations thereof, can furthermore be arranged between the substrate and the component.
  • the electronic component is optionally arranged on a carrier, for example by gluing, soldering and / or flip-chip technology.
  • the semiconductor sensor according to the invention is outstandingly suitable for relative and absolute measurements of chemical and / or physical parameters.
  • two similar sensors can be placed together on a substrate or carrier.
  • several signals can be obtained over which possibly can be telt.
  • Another possibility is to cover one of the sensors arranged in this way on its sensitive surface with an inert material. Consequently, this sensor is not influenced by the medium and can therefore be used to determine other variables which are not relevant to the sensor, for example for determining the temperature and its influence on the sensor signal.
  • the sensors according to the invention are particularly suitable for determining the H + / H 3 O + concentration or the OH ' concentration, ie as pH sensors or for determining the O 2 concentration, ie as oxygen sensors.
  • the sensors according to the invention are suitable not only for the measurement in the range of room temperature, but in particular also at higher temperatures between
  • FIG. 1 shows a semiconductor sensor according to the invention
  • FIG. 2 shows a cross section of a corresponding semiconductor sensor according to the invention
  • FIG. 4 shows a cross section through a further sensor according to the invention
  • FIG. 5 shows a cross section through a further sensor according to the invention
  • FIG. 6 shows a cross section and a plan view of a further sensor according to the invention with a plurality of sensor elements
  • FIG. 7 shows the plan view of a further semiconductor sensor according to the invention.
  • FIG. 1 shows a semiconductor sensor 1 as an ion sensor in cross section in plan view.
  • the semiconductor sensor 1 comprises a semiconductor material 3. On the side of two opposite sides of the cross-sectionally rectangular semiconductor material 4 there are electrical contacts 5a, 5b against which the generated sensor signal is applied. These contacts 5a and 5b are typically ohmic contacts, but may also be made as blocking contacts.
  • the semiconductor material 3 is packed with a material 6 which is resistant to the medium to be measured and additionally insulating. For this purpose can For example, an epoxy resin can be used. Only the region 8 is recessed from this insulation, so that the region 8 represents an opening in which the semiconductor material may come into contact with the medium to be examined. In this region 8, however, the semiconductor material is coated with a functional layer 4, so that this contact is only indirect.
  • the material of this functional layer 4 is as chemically inert as possible and impermeable to ions.
  • impermeable layer systems are preferred for ions, which for a single-layer system means an ion-impermeable layer, whereas in multilayer systems only at least one or individual layers should be impermeable at least to the ions to be determined, while other layers should be partially or completely permeable to ions or other substances.
  • the mode of functioning of the functional layer 4 can be explained as follows: It is intended to allow a chemical binding of ions from the medium to be investigated, but to completely or partially prevent the passage onto the semiconductor surface.
  • the chemical bond causes the conversion of the chemical concentration of at least one component of the medium into an electrical variable, such as the potential at the surface of the functional layer, and consequently results in an electrical parameter (such as the polarization). Tential) on the semiconductor surface of the device itself. This acts on the semiconductor and is exploited to cause an electrical change (for example, the charge carrier density or space charge zone and thus ultimately the current and / or the capacitance) in the semiconductor.
  • various materials such as oxides, nitrides, metals or ceramics as well as the respective oxides, mixtures, stoichiometric or non-stoichiometric compounds or alloys can be used.
  • This functional layer sequence preferably consists of a multilayer system, each layer assuming specific tasks.
  • a three-layer system can be selected in which the lowermost layer (directly in contact with the semiconductor) serves as adhesion promoter (may be, for example, titanium or Al or TiW, Si, polymer, or the like).
  • the middle layer is chosen so as to prevent diffusion of at least some or even all ions to the semiconductor surface.
  • the uppermost layer in direct contact with the medium under investigation) can be freely selected, "erzrelen ⁇ .
  • Layers are chosen to be at least as high that their function is fulfilled, but as thin as possible to ensure a low-loss potential transfer to the semiconductor surface. Likewise, these layers can be structured to be targeted in specific areas from the surface make individual layers accessible (for example, to make electrical contact with a layer).
  • titanium oxide applied by sputtering deposition or electrochemical deposition as well as by subsequent oxidation of titanium layers with thicknesses between 5 nm and 20 nm applied to the semiconductor surface achieves a functionality of the sensors specifically for determining pH values.
  • the layers produced by subsequent oxidation need not have a stoichiometric compound or, preferably, in a particular one
  • Crystallinity may be present, but may, for example, preferably characterized by an excess of a component (such as oxygen or nitrogen over the metal). This can be specifically exploited to set about the dielectric constant or the electrical resistance.
  • a component such as oxygen or nitrogen over the metal
  • the electrically active layer 3 consists, for example, of at least two layers: a lower GaN and an upper AlGaN layer. Structures with a comparatively low Al content x between 1% and 15%, which are typical for conventional AlGaN / GaN transistors, are preferred with a small thickness of the AlGaN layer (typically between 0 and 20 nm, otherwise 20 to 30 nm).
  • the lower Al content leads to moderate charge carrier layer concentrations (not in the 10 13 cm "2 range as usual, but in the
  • the smaller thickness is due to its influence on the conduction band discontinuity with responsible for the comparatively lower charge carrier On the whole, a higher sensitivity of the semiconductor component to potential changes at the surface can be achieved.
  • these are, for example, structures in the material system GaN or diamond, which a) are either low-volume-doped (activated Charge carrier concentration in the range below 5 ⁇ 10 17 cm -3 ) with a thickness of the electrically active layer 3 in the range 10 to 500 nm or b) pulse doping (with activated charge carrier layer concentration in the range below
  • the distance to the semiconductor surface should be in the range 2 nm to 20 nm in order to achieve a high sensitivity.
  • the functional layer sequence 4 itself does not serve as gate insulator or gate oxide, as is the case, for example, with a silicon MOS system used in classical ISFET or CHEMFET applications.
  • the gate oxide in such silicon systems is imperative for the device function itself.
  • the functional layer is decoupled from the function of the electronic component implemented in the semiconductor material 3.
  • the sensitive surface is not directly regarded as a gate electrode or only in connection with the medium to be measured. Because this determines, for example, in a pH sensor, the proportion of OH " - or H + ions and thus the potential applied to the surface of the functional layer 4. This potential in turn determines the current flow between, for example, the source electrode and the drain electrode of the electronic component. It is therefore also possible with the aid of an electrode, for example of platinum, to apply an additional potential to the surface via the solution in order to control the electronic component, for example a field-effect transistor, or to define an operating point. In this case, a reference electrode is preferably used whose potential is always constant with respect to the solution.
  • the functional layer is advantageously titanium oxide in this example.
  • the encapsulation of the sensor with the outer insulation 6 is not required everywhere, especially not if the material properties of the semiconductor material 3 permit this in whole or in part. It may then be sufficient to apply the cover 6 only to the required areas, for example only to the areas surrounding the contact area 8 or to the terminals 5a, 5b.
  • the shape of the electrical contacts 5a, 5b can be adapted to the respective measurement method.
  • the basic form consists of a rectangular format for the contacts 5a, 5b, as can be seen in FIG.
  • a round structure may also be preferred.
  • Even acute-angled or point-shaped contact geometries can be used, for example, to generate targeted local high-field zones of an electric field.
  • the entire sensor 1 can in turn be arranged on a support. This can be done for example by gluing, soldering or flip-chip technology. This then allows integration into a circuit.
  • conductive traces may then be used on a substrate material that is communicated by a technique such as lithography be contacted with the contacts 5a and 5b with metallization, gluing, soldering, bonding or the like in order to produce an electrical contact from the sensor 1 to the measuring environment or to the evaluation electronics.
  • a counterelectrode is dispensed with in the determination of the pH, since the counterelectrode may itself have a pH dependency and thus an accurate determination of the pH value is not possible.
  • a reference electrode that is pH independent can be used regardless of how the pH sensor is wired.
  • the reference electrode always has the same potential with respect to a solution, regardless of the pH of the solution. With the help of such a reference sensor and the pH sensor, the pH of an unknown solution can then be determined.
  • a counter electrode is therefore only needed if the transistor is to be controlled via the solution or to characterize the pH sensor. However, this always takes place with a known pH solution.
  • the change in the drain-source current can be measured with a constant drain-source voltage.
  • the change in the drain-source voltage can be measured with a constant drain-source current.
  • FIG. 2 shows a further example of a sensor according to the invention. This is now shown in cross section, so that the layer structure can be seen below the functional layer 4.
  • a substrate 2 which in this example consists of silicon, sapphire, silicon carbide, diamond or iridium
  • a buffer layer 9 for example of gallium nitride, aluminum nitride, aluminum gallium nitride or diamond.
  • Another layer sequence 3 for example GaN / AlGaN / GaN or doped GaN forms the electronic component.
  • the electrical contact structures 5a, 5b which laterally delimit a functional layer sequence 4 of several layers.
  • FIG. 3 shows a vertical structure of a sensor, the layer sequence corresponding to that in FIG.
  • Such a vertical structure can be used, for example, in the case of bipolar transistors SiT or the like.
  • the electrical contacts 5a, 5b are therefore preferably located on the top or bottom side or top and bottom or etched structures on one side, but in different layers or etch depths. A deep etching of local areas of the top and bottom of the layer sequence can also be used.
  • the layer sequence of the layer substrate 2, buffer 9, semiconductor 3 and layer sequence 4a is corresponding to that in FIG.
  • the layer sequence 4a has an adjacent layer sequence 4b which extends in the vertical direction.
  • the contact 5a essentially contacts the buffer layer 9 and the layer sequence 4b, while the contact 5b contacts the electronic component 3 and the layer sequence 4a.
  • FIG. 5 shows a further sensor structure in which again the layer sequence comprising substrate 2, buffer 9 and semiconductor material 3 as well as layer sequence 4 corresponds to that in FIG.
  • the contacts 5a and 5b are also arranged as shown in FIG. 2 laterally of the layer sequence 4. However, they are connected to electrical connections 12a, 12b, which in turn are introduced into the layer sequence in the vertical direction. In this way it is possible to contact the sensor on its side facing away from the sensitive surface and the opening 8.
  • Such backside contact enables the con- timing and placement of the sensor on a board or carrier, without having to provide contacts on the front of the sensor. It is thus possible here to contact directly on the board or carrier applied electrical lines, such as conductors of a printed circuit board.
  • FIG. 6 shows, in sub-images A and B, a further sensor according to the invention which has individual sensor elements.
  • Figure 6A is a cross section in
  • the sensor has a total of three sensor elements 10a, 10b and 10c, which are connected via electrical lines 12a, 12b, 12c and 12d to contacts 5a, 5b, 5c and 5d.
  • the contact 5d is grounded, while the contacts 5a, 5b and 5c can be connected to a voltage source.
  • the geometries of the sensor elements 10a, 10b, 10c, which are formed by the sensitive surfaces of the functional layers 4 according to the invention, are different in size in the example shown in FIG. They may also be different in terms of other properties, so that the individual sensor elements respond to different ions or substances in still different ways.
  • the individual sensor elements can thus have the same function or different functions (sensitivity, sensitivity, etc.).
  • the surface of the sensor 1 is largely covered with an electrically insulating material 6. Not covered by the material 6 are the contacts 5a, 5b, 5c and 5d, as well as the openings 8a, 8b and 8c, which provide access to the medium Sensor elements 10a, 10b and 10c allow.
  • the overall dimension of the sensor element array 1 in the present example is 5 mm ⁇ 5 mm, while the sensor surfaces, which are defined by the sizes of the opening 8a,
  • a polyimide was used in this example.
  • the present invention enables a tremendous miniaturization of the sensors and thus also a duplication of the measurement options.
  • FIG. 7 shows a further sensor which is similar to that in FIG. In contrast to the sensor shown in FIG. 6B, however, the opening 8c of the sensor element 10c is covered. This shows that
  • Sensor element 10c no media sensitivity and is a blind sensor. However, with respect to all other parameters, this dummy sensor element has the same structure and structure as a normal sensor.
  • the sensor element 10c By means of the sensor element 10c it is now possible to determine changes in the sensor sensitivity of the sensor elements 10a and 10b etc. due to temperature change or other factors and to calibrate the normal sensor elements 10a and 10b or their signals measuring the medium accordingly. By means of this blind sample by means of the covered sensor element 10c, it is thus possible to compensate for other disturbing influences.

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  • Life Sciences & Earth Sciences (AREA)
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  • Health & Medical Sciences (AREA)
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Abstract

L'invention concerne un capteur à semi-conducteurs servant à déterminer des propriétés physiques et/ou chimiques d'un fluide, en particulier un capteur de pH. Ce capteur comprend un composant électronique présentant une surface sensible, ce composant électronique (3) étant composé de semi-conducteurs à large écart énergétique. Selon l'invention, la surface sensible est recouverte au moins partiellement d'une série de couches fonctionnelles qui présente une surface sensible aux ions opposée à la surface sensible du composant électronique et qui est recouverte d'au moins une couche, ladite série de couches fonctionnelles (4) étant imperméable au moins au fluide et/ou aux ions ou aux substances à analyser.
EP06776682A 2005-08-08 2006-08-08 Capteur a semi-conducteurs a large ecart energetique presentant une couche superieure isolante Withdrawn EP1913372A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005037276 2005-08-08
PCT/EP2006/007846 WO2007017252A1 (fr) 2005-08-08 2006-08-08 Capteur a semi-conducteurs a large ecart energetique presentant une couche superieure isolante

Publications (1)

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EP1913372A1 true EP1913372A1 (fr) 2008-04-23

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US (1) US8129725B2 (fr)
EP (1) EP1913372A1 (fr)
JP (2) JP2009505045A (fr)
WO (1) WO2007017252A1 (fr)

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JP2012198250A (ja) 2012-10-18
US8129725B2 (en) 2012-03-06
US20100133547A1 (en) 2010-06-03
WO2007017252A1 (fr) 2007-02-15

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