Tag Archives: halides

Photo-chemical Fascinations, Part 2: Valence Bands & Parking Lots

Previously, we talked just a little bit about halides, and how they fit into the formation of silver gelatin-based images. Today, we’re going to take a closer look at part of the “how.”

Let’s begin with a brief overview of the darkroom process. As a reminder, the mechanics of creating a black and white print generally include the following steps:

  1. A paper is pre-coated with a halide salt and silver nitrate that are mixed in a binder such as gelatin.
  2. An image is first generated by projecting a source of illumination (like the sun or a lamp) through film onto a coated piece of paper. 
  3. Next, the paper or film is developed in a bath of chemicals.  This is the part of the process the image seems to “magically” appear!
  4. The image developing chemical reaction is stopped in a “stop bath.”
  5. The paper or film is moved to a second bath to “fix” the image in a fixative bath.
  6. The photograph is rinsed and hung to dry – ready to safely see the light of day.

Now, let’s delve a little deeper into the chemical reaction described in step two, beginning with a bit of a thought experiment. If I say to you, “semiconductor,” what springs to mind? Something involving electronics, perhaps? Maybe chips, lots of little circuits and tiny wires? Maybe, if you’re more photography-minded, a digital camera? All excellent things to think of! With this in mind, what if I told you that our silver gelatin emulsion is also a semiconductor, one that converts light into latent images instead of electricity?

Well, that is what we’re going to explore today, the basics of the mechanism by which light gets our emulsion ready to record latent images. The light shines on an atom (in this case, our silver halide ion), energy is transferred to an electron, and the electron moves to an excited state and is ready to make chemical magic.

If you refer back to your basic chemistry, atoms are composed of three parts: protons, neutrons, and electrons. Protons are positively charged and reside in the nucleus (center) of an atom with chargeless neutrons. Negatively charged electrons orbit the nucleus in bands. When all things are equal, an atom has the same number of protons as electrons, leaving the atom neutral. There aren’t a lot of atoms that are naturally like this, however; an atom will often have too many or too few electrons in orbit. This is a good thing, as it not only makes them stable, it makes them available for bonding with other atoms and creating chemical reactions.

Now let’s apply some of that to our silver halide. The electrons near the nucleus of our ion are in the “ground” state. They’re unexcited. The nucleus has them firmly gripped in its gravitational pull and they’re uninterested in going anywhere. This area of grounded electrons is known as the valence band. In order for them to be available for any sort of exchange, they’ll need to get farther away from that nucleus, and out into an outer band of the ion, conveniently known as the conductance band.

How does this all relate to the parking lots I mentioned in the title? I’m glad you asked. The parking lot analogy is a fantastic illustration of the process by which light interacts with matter. Let’s think of it this way: the nucleus of the silver halide ion is your typical Big Box Store. Directly outside of the store is the valence band parking lot, full of electron cars, all off, all waiting in the ground state. Beyond the parking lot is a strip of grass, which we’ll get to shortly, and beyond that is the conductance band (i.e, the road), where the cars are all in motion, on their way to any number of places.

Valance Bands illustration
The parking lot analogy, illustrated, from AIC’s Photographic Chemistry for Preservation, unit 2, “The Latent Image.”

In order for the cars to get out of the valence band, they’re going to need some energy. For our electrons, the needed energy is light. Once they get light to get the engines going, they can pull out of the parking lot and onto the road and drive off to chemical reactions.

Now let’s detour briefly to that grassy strip that I mentioned earlier. It’s known as the forbidden gap. Ideally, this area is empty. However, due to defects such as insufficient energy, an electron may not be able to completely cross to the conductance band, and may be temporarily stuck in this gap. Even here they can be useful as stepping stones for other electrons that need to cross over. Stuck electrons will either receive more energy to get them to the outer bands, or they’ll lose energy and be pulled back to the valence band.

I’ll note here that this structure is characteristic of all semiconductors, including digital camera sensors. In silver halide grains, this excitement of electrons will always happen when it comes into contact with light, as silver halide has a light sensitivity of 100%. No matter what, when a grain of silver halide is exposed to light, it will always liberate an electron. You also needn’t think of it as just one electron at a time being excited in this fashion. The grain can have so much energy that its valence band is completely empty, and vice versa.

What happens after this? Well, that’s an exploration for next time.

Hyacinth Tucker (UCL) — Bindery and Conservation Technician

Bite-Sized Takeaways From Photographic Chemistry Study

Introduction and a Little Something About Halides

About two years ago, I set upon a mission to gain expertise in the area of identification and treatment of photographic materials. Under the guidance of our conservator, Ashleigh, I developed an education plan that was split between the theory of learning the ins and outs of photograph identification, and the hands-on work of treating pieces that came into the Lab. Of course, these two things go hand in hand. If you can’t identify a piece, you can’t treat it correctly, right?

Fast forward to last year. With the start of the pandemic and the transition to working from home, my education plan changed radically. If I’m not in the Lab, I can’t spend much time on treatment, so I had to get a little creative and work on other ways to learn more.

Enter the American Institute for Conservation’s self-study series on Photographic Chemistry for Preservation. It involves eight fairly in-depth units on silver-based analog photographs, how they are created, and as a consequence, how they age and deteriorate.  

I am about halfway through the series; a triumph for me, as I have never been one for the study of chemistry. I will say that while it is still very technical, I’ve had a lot of good pegs to hang the information on, owing both to my earlier studies in photograph conservation and my personal history with film photography. It’s been a tremendous thing, viewing things that I learned as a photography student from a different angle. So far, it’s been a great journey. 

In this series, I will share with you some of the most fascinating things that I’ve learned so far. My aim will be to keep the technical as simple as possible, for those of you who are like me, still coming to terms with the deeper science. The small bites help it all make sense, I promise. Hopefully, you’ll find it all as interesting as I have.  

Before we can understand anything else, we need to talk about halides. What are those and why are they used in photography? Good questions! Halide salts are derived from halogens, which occupy group 7A (column 17) of the Periodic Table of Elements (see below.) Halide salts are used in photographic emulsions that are spread over a substrate (such as paper or film) before the substrate is exposed to light. The silver halides react to the light to form an image when developed.  

I should note here that silver gelatin prints, albumen, and collodion photographs all utilize silver halides in their chemical composition. However, silver gelatin is unique among the three in that it is the only one that uses a true emulsion; in albumen and collodion coatings, the halides rest on the surface.  

  • Photograph – silver gelatin process
  • Photograph – albumin process
  • Photograph – collodion process

In forming the silver gelatin emulsion, halide salts are combined with silver nitrate and water to form silver halides, the compound at the core of silver gelatin photography. Silver nitrate is pretty much universally used regardless of halide salt, as it is water soluble (it dissolves) but not too much so. The freed silver will look for a bond partner, and the halides in halide salt fits the bill.  As a result, silver nitrate, when combined with a halide salt in water, will result in silver halide and a left over salt.  

This reaction, which seems like a lot, I know, is referred to for our purposes as “The Emulsification Equation.” To refresh our memories a bit, an emulsification is a liquid (here, gelatin) that contains fine particles of another liquid (the silver halide) without fully combining. Think mayonnaise, or butter. (This isn’t perfectly analogous, as silver halides are crystalline solids and not liquid fats, but the basic idea is the same.) 

Chemically speaking, that reaction looks like this: 

Equation for emulsification

As a quick reminder, Ag = silver, N = Nitrogen, O = Oxygen, K = Potassium, and Cl = Chlorine. 

Now, if you’ll look at the image of the halogen column of the table below, you’ll see a number of options for salts to combine with silver nitrate. Older emulsions involved bromine or iodine; more modern emulsions tend toward chlorine. Crystals formed from silver chloride salts are much more uniform in structure, which makes its use outcomes much more predictable.  

Salts that will combine with silver nitrate

I’m sure you’ve noticed that we’ve got a couple of halogens unaccounted for, namely fluorine and astatine. Neither of these are used for this kind of work, and for good reason. Fluorine, for its part, is very water soluble. Very water soluble. To put it in perspective, sodium chloride (regular table salt) is about 35% water soluble. I’m sure that in the course of cooking, we’ve all dissolved salt in water, and you can recall how relatively simple that is to do, though not without some small effort. Well, fluorine salts are about 172% water soluble! You could use it for your emulsion, but moments after developing an image in a water-based solution, you’d see it dissolve before your eyes.  

I’ll note here very briefly that chlorine, bromine, and iodine are also more soluble than table salt, but not nearly as much as fluorine, making them perfect partners for our silver ions.

Meanwhile, astatine is…well, it’s radioactive. I think you can see the problem with this one.  

And there you have it, a short and hopefully painless explanation of the humble halide in silver-based photography. In the coming months, we’ll be looking at other fascinating aspects of halides and our Emulsification Equation.  

Hyacinth Tucker (UCL) —- Bindery and Conservation Technician